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 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 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.
• EO ethylene oxide
• 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.
• formulations defined above were found in formulations for machine dishwashing, in short also called preparations used in the invention.
• 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 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.
• 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
• polyether (a1.3) is a diol.
• 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).
• 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.
• 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, 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).
• 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.
• 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.
• EO ethylene oxide
• 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
• C 12 -C 18 alcohols ethoxylated with an average of 5 moles of EO per mole of alkanol.
• 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.
• 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.
• 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.
• 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 aides, disintegrating agents, 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.
• suitable surfactants (b) are selected from ethoxylated or propoxylated sorbitan esters.
• amine oxides or alkyl glycosides are also suitable.
• formulations used according to the invention comprise a mixture of several different surfactants (b).
• 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.
• 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.
• 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.
• 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.
• 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 salt
• 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 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.
• 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 ,
• 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.
• 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.
• 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.
• 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 up to 60% by weight of builder (f) or cobuilder (f), for example in the range from 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.
• carboxymethyloxysuccinates tartrate monosuccinate, tartrate disuccinate, tartrate mono
• builders suitable (f) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layer silicates, particularly those having the formula ⁇ -Na 2 Si 2 O 5, ⁇ -Na 2 Si 2 O 5, and ⁇ -Na 2 Si 2 O 5 .
• cobuilders (f) are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
• hydroxyalkane phosphonates preference is given to 1-hydroxyethane-1,1-diphosphonate (HEDP) 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.
• carbonates and bicarbonates are used, of which the alkali metal salts, in particular sodium salts, are preferred, for example sodium carbonate and sodium bicarbonate.
• 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, 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- ⁇ -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 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).
• MMA salts N-methylmorpholinium acetonitrile salts
• DADHT 1,5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine
• 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.
• 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.
• 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.
• 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.
• the formulations used in the invention may contain one or more preservatives, for example, 2-methyl-2 H- isothiazol-3-one (Kathon CG).
• preservatives for example, 2-methyl-2 H- 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.
• tablette 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).
• 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.
• 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).
• 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 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.
• 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 separately melted, 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 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.
• the dry copolymer (a1) is recovered 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 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.
• Compounds of the general formula (I) can be obtained by alkoxylation of the corresponding C 8 -C 24 -alcohols with alkylene oxides.
• 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.
• alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides
• 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.
• 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.
• 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, together or separately, simultaneously or in succession ,
• 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 with 67.90 g of ethyl acetate
• 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
• the alkoxylate (a2-1) used was: nC 18 H 37 - (OCH 2 CH 2 ) 9 -OH
• 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).
• 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.
• Table 4 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

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