Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers

Definitions

• the present invention relates to the use of preparations containing
• R 2 is 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 is a number in the range of 1 to 100, in formulations for automatic dishwashing.
• the present invention relates to the use of certain copolymers.
• 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 generally customary further constituents, to improve the Rinse power in phosphate-containing and in 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.
• EO ethylene oxide
• preparations defined at the outset has been found in formulations for machine dishwashing, in short also termed preparations used according to the invention.
• copolymer (a1) at least one copolymer, also called copolymer (a1) for short.
• Copolymer (a1) is obtainable by copolymerization of
• N-vinylamide for example N-vinylformamide or N-
• Vinylacetamide preferably at least one N-vinyllactam, for example N-vinylpyrrolidone and N-vinylcaprolactam,
• 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.
• 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 of which AB type or ABA may be used. Be a type.
• Polyether (a1.3) can be etherified on one or both sides with C 1 -C 20 -alkanol or an alkylating agent, in each case identically or differently, preferably with C 1 -C 6 -alkanol, for example with methanol, ethanol, n-butanol, isopropanol, n- Propanol, isobutanol, n-pentanol, n-hexanol, n-octanol, n-nonanol, n-decanol, n-dodecyl, n-tridecanol, n-hexadecanol or n-octadecanol.
• C 1 -C 20 -alkanol or an alkylating agent in each case identically or differently, preferably with C 1 -C 6 -alkanol, for example with methanol, ethanol, n-butanol, isoprop
• polyether (a1.3) is a diol.
• polyether (a1.3) has an average molecular weight M w in the range from 1 .000 to 100,000 g / mol, preferably 1,500 to 35,000 g / mol, particularly preferably 10,000 g / mol.
• the mean molecular weights M w are determined on the basis of the OH number measured according to DIN 53240 or by gel permeation chromatography (GPC).
• 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, for example by free-radical copolymerization.
• 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).
• 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.
• 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.
• copolymer (a1) comprises copolymerized in total: in the range from 30 to 80% by weight, preferably 40 to 70% by weight, more preferably 50 to 60% by weight, of N-vinylamide (a1 .1 ),
• polyether 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),
• R 1 is 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 is 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, particularly 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, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, more preferably methyl or n-butyl, m is a number in
• 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 statically distributed or blockwise arranged 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.
• Particularly preferred are alkoxylates of alcohols of native origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol, ethoxylated with an average of 2 to 8 moles of EO per mole of C8-Ci8-alkanol.
• Ci2-Ci4-alkanols ethoxylated with an average of 3 or 4 moles of EO per mole of alkanol
• Cg-Cn-alkanols ethoxylated with an average of 7 moles of EO per mole of alkanol
• C3-Cis alcohols ethoxylated with an average of 3, 5, 7 or 8 moles of EO per mole of alkanol
• Ci2-Ci8 alcohols ethoxylated with an average of 5 moles of EO per mole of alkanol.
• Iso-Cio-alcohols alkoxylated with 10 mol of ethylene oxide and on average 1, 5 mol of 1, 2-pentenoxide, C10- to C22 fatty alcohols alkoxylated with 9 moles of ethylene oxide and 5 moles of propylene oxide, C13- to Ci5-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,
• alkoxylates of the formula (I) are ethoxylates of the formula (II) R 1 - (OCH 2 CH 2 ) x-OR 3 (II) with
• R 1 is a linear Ci6-Ci8-alkyl radical
• R 3 is linear or branched C 1 -C 6 -alkyl or preferably hydrogen
• ethoxylates of the formula (II) are those based on tallow fatty alcohols (C 16-18 alcohols) with an average of 9 mol of ethylene oxide per mole of tallow fatty alcohol.
• Preferred linear Ci6-Ci8-alkanols are n-hexadecanol and n-octadecanol. These can be obtained by hydrogenation of natural tallow fat.
• the linear Ci7 alkanol is also suitable. Mixtures of linear Ci6- and cis-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 Ci6- and Cis 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, it is preferable to subsume tallow fatty alcohols because of the only slight contamination with unsaturated alkanols under C 16-18 alkanols.
• 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).
• copolymer (a1) and alkoxylate (a2) are present as solid solution in preparations used according to the invention.
• 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.
• preparations (a) used according to the invention are present as free-flowing and flowable water-soluble powders.
• preparations (a) used according to the invention are present as powders having a mean particle diameter in the range from 100 to 1500 ⁇ m. In another embodiment of the present invention, preparations (a) used according to the invention are present as granules.
• 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.
• 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.
• formulations used according to the invention contain:
• used preparation preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%.
• surfactant (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,
• polycarboxylate (c) in total in the range from 0 to 20% by weight of one or more polycarboxylates, also called polycarboxylate (c) for short,
• complexing agents (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,
• bleach (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,
• Data in% by weight are based on the total solids content of the formulation used according to the invention.
• formulations used according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.
• 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.
• 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.
• additives (i) are selected from anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tabletting aids, disintegrants, thickeners and solubilizers.
• 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.
• 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).
• surfactant (b) is selected from di- and multiblock copolymers composed of C 1 -C 20 -alkanol, ethylene oxide and propylene oxide.
• 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.
• 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.
• formulations used according to the invention comprise a mixture of several different surfactants (b).
• the preparation used according to the invention contains 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 polycarboxylate (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 citraaconic 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.
• copolymeric polycarboxylates (c) in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
• 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 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene with 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 which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
• the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
• Particularly preferred monomers containing sulfonic acid groups 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
• Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
• 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.
• aminocarboxylates are understood to mean nitrilotriacetic acid and those organic compounds which have a tertiary amino group which has one or two Ch-COOH groups which, as mentioned above, can be partially or completely neutralized.
• polyaminocarboxylates are understood as meaning those organic compounds which have at least two tertiary amino groups which independently of one another each contain one or two
• Ch have -COOH groups, which - as mentioned above - can be partially or completely neutralized or can.
• aminocarboxylates are selected from those organic compounds having a secondary amino group having one or two CH (COOH) CH 2 -COOH group (s) partially or completely neutralized as mentioned above can or can.
• 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.
• 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, especially their salts Potassium and sodium salts.
• Particularly preferred complexing agents (d) are methylglycinediacetic acid and its salts.
• 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.
• 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.
• 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.
• 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.
• the formulation used according to the invention may contain in the range of up to 60% by weight of builder (f) or cobuilder (f), for example in the range of 0.1 to 60% by weight.
• 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, ⁇ -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 ⁇ -hydroxypropionic acid.
• suitable builders (f) are furthermore succinic acid and its alkali metal salts,
• Suitable builders (f) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, in particular those of the formula a-Na 2 Si 2 O, ⁇ -Na 2 Si 2 O 5 , and 5-Na 2 Si 2 O 5 .
• cobuilders (f) are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
• hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is preferred as co-builder (f).
• HEDP 1-hydroxyethane-1,1-diphosphonate
• 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.
• formulations used in the invention contain up to 30% by weight of bleach (g) and optionally one or more bleach activators or bleach catalysts.
• formulations used according to the invention contain one or more oxygen bleaches or one or more chlorine-containing bleaches.
• oxygen bleaching agents are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-a-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.
• 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-maucetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2- dioxo-hexahydro-1,3,5-triazine (“DADHT”) or nitrile quats, ie trimethylammonium acetonitrile salt (s).
• MMA salts N-methylmorpholinium acetonitrile salts
• DADHT 1,5-diacetyl-2,2- dioxo-hexahydro-1,3,5-triazine
• nitrile quats ie trimethylammonium acetonitrile salt (s).
• 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.
• 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.
• enzymes (h) are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
• formulations used according to the invention may contain in total from 0.1 to 50% by weight of one or more additives (i).
• 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.
• 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.
• 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 has a C 6 -C 20 -alkylene radical, preferably a Cs-CIS radical.
• Alkylene radical bearing 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 compounds are alkali metal carbonates, alkali metal hydroxycarbonates, alkali metal hydroxides and alkali metal metasilicates.
• Preferred alkali metal is in each case potassium, particularly preferred is sodium.
• Formulations used according to the invention may contain one or more corrosion inhibitors.
• corrosion inhibitors such compounds that inhibit the corrosion of metal.
• suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles Phenol derivatives such as hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol.
• formulations used in the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.
• 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.
• formulations used according to the invention generally contain in the range from 0.05 to 0.5% by weight defoamer.
• formulations used according to the invention may contain one or more acids, for example methanesulfonic acid or its salts.
• formulations used according to the invention may comprise one or more dyes.
• An example of a suitable dye is patent blue.
• formulations used according to the invention may contain one or more perfumes, for example a perfume.
• formulations used according to the invention may contain one or more preservatives, for example 2-methyl-2H-isothiazol-3-one (Kathon CG).
• a suitable filler is, for example, sodium sulfate.
• 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.
• 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.
• Machine dishwashing is preferably dishwashing with a dishwasher.
• water having a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH, is used for cleaning, which is to be understood in particular as 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.
• Another object of the present invention is the use of copolymer (a1) obtainable by copolymerization of
• copolymer (a1) is obtainable by copolymerization of a total of in the range of 30 to 80% by weight of N-vinylamide (a1 .1),
• copolymer (a1) in total in the range from 10 to 50% by weight of polyethers (a1 .3), total in the range of zero to 10 wt .-% comonomer (e) (a1.4), each 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.
• 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.
• the procedure is to mix at least one copolymer (a1) and at least one alkoxylate (a2) in each case in the molten state and then allow it to cool.
• 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.
• 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.
• 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.
• 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.
• 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.
• copolymer (a1) and alkoxylate (a2) are melted separately, the two melts are mixed and then allowed to cool.
• melt-liquid copolymer (a1) as obtained after the purification operations following its preparation, in a further step.
• 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).
• 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).
• the extruder screw should be provided with suitable Mischele- 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.
• the recovery of the dry copolymer (a1) takes place in the presence of alkoxylate (a2).
• 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.
• the nonionic surfactant (a2) may be introduced into the extruder cold as a solid or liquid and the polymer solution may be pumped out, and both degassed together, or the polymer solution is introduced, ie pumped into the heated extruder and first evaporates some of the polymer Solvent (for example 50-95%) and then at a later stage, the nonionic surfactant (a2) or solid as a slurry and evaporates solvent together.
• 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.
• R 2 is hydrogen
• the alkoxylation can be, for example, using alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides or with acid catalysts such as BF 3 ⁇ H3PO4, BF 3 ⁇ 2 (C 2 H 5) 20, BF 3, SbCl 5, SnCl 4 ⁇ 2H 2 0 or hydrotalcite, or with double metal cyanide perform catalysts.
• alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides
• acid catalysts such as BF 3 ⁇ H3PO4, BF 3 ⁇ 2 (C 2 H 5) 20, BF 3, SbCl 5, SnCl 4 ⁇ 2H 2 0 or hydrotalcite, or with double metal cyanide perform catalysts.
• 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 nonaqueous organic solvents are, for example, alcohols, such as methanol, ethanol, n-propanol, and isopropanol and also glycols, such as ethylene glycol and glycerol.
• suitable solvents are esters such as, for example, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butyl acetate, ethyl acetate being preferred.
• polyethers (a1.3) are preferably added, and N-vinylamide (a1.1), vinyl acetate (a1.2) and optionally further comonomer (a1.4) are added, jointly or separately, simultaneously or one after the other.
• the free radical copolymerization is preferably carried out at temperatures of 60 to 100 ° C.
• suitable pressure is normal pressure, but one can also choose higher or lower pressure.
• 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 at 67.90 g
• 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
• polycarboxylate (c-1) 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).
• HEDP disodium salt of hydroxyethane- (1, 1-diphosphonic acid
• 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 cloudy 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.
• Dishwashing detergent 21 g

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