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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0073—Anticorrosion compositions
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/02—Preparation in the form of powder by spray drying
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • 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
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • 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
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/18—Glass; Plastics

Definitions

• the present invention relates to formulations containing
• A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof, and (B) at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range of 500 to below 800 g / mol, which has a positive charge density of at least 5 meq / g and which has in the range from 2 to a maximum of 80 wt .-% alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer.
• MGDA methylglycine diacetate
• IDDS iminodisuccinic acid
• GLDA glutamic acid diacetate
• the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing agents, in particular dishwasher detergents for automatic dishwashing.
• Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.
• Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences.
• certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
• Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
• WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents.
• Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example.
• WO 01/96516 proposes formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used. From WO 2010/020765 dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. However, glass corrosion, in particular line corrosion and turbidity, is in many cases not sufficiently delayed or prevented.
• Formulations of the invention are heavy metal-free. This is to be understood in the context of the present invention that formulations according to the invention are free of those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and bismuth. In the context of the present invention, "free from” is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on The formulation according to the invention preferably has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.
• heavy metals are all metals having a specific density of at least 6 g / cm 3.
• heavy metals are noble metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
• formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm. Contain formulations according to the invention
• A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof, in the context of the present invention also referred to as aminocarboxylate (A) or compound (A), and preferably their salts.
• MGDA methylglycine diacetate
• IDS iminodisuccinic acid
• GLDA glutamic acid diacetate
• inorganic cations for example ammonium, alkali or alkaline earth metal, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
• inorganic cations for example ammonium, alkali or alkaline earth metal, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C
• Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GL DA).
• MGDA methylglycine diacetate
• IDS iminodisuccinic acid
• GL DA glutamic acid diacetate
• MGDA methylglycine diacetate
• IDS iminodisuccinic acid
• GLDA glutamic acid diacetate
• Formulations according to the invention also contain
• modified alkyleneimine polymers are also briefly referred to as modified polyalkyleneimine (B) in the context of the present invention.
• alkyleneimine polymers are to be understood as meaning those polymeric materials which are obtained by homo- or copolymerization of one or more cyclic imines or by grafting a (co) polymer with at least one cyclic imine.
• examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine.
• polyalkylene polyamines are preferably understood as meaning those polymers which contain at least six nitrogen atoms and at least five C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule, for example pentaethylenehexamine, and in particular polyethyleneimines.
• Alkyleneimine polymer and in particular polyethylenimine may, for example, have an average molecular weight (M w ) of at least 300 g / mol, preferably the average molecular weight of polyethylenimine is in the range from 350 to 750, particularly preferably 400 to 500 g / mol, determined by light scattering.
• Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as Alkylenimin- polymer.
• Suitable quaternizing agents are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chloride, such as methyl chloride, methyl bromide, mid, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride.
• alkyl halides in particular C 1 -C 10 -alkyl chloride, such as methyl chloride, methyl bromide, mid, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl s
• the degree of quaternization (alkylation) is preferably 1 to 25, particularly preferably up to 20 mol%, based on quaternizable (alkylatable) N atoms in alkyleneimine. Polymer.
• polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers.
• Suitable polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain from 3 to 10 basic nitrogen atoms in the molecule.
• suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the abovementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid.
• Adipic acid is preferably used for the preparation of polyamidoamines.
• Suitable polyalkylenepolyamines which are condensed with the abovementioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
• the abovementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamine.
• the preparation of polyamidoamine is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate.
• the condensation of dicarboxylic acid with polyalkylenepolyamine takes place at higher temperatures, for example in the range from 120 to 220.degree.
• the water formed during the reaction is distilled off from the reaction mixture.
• the condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms.
• lactones or lactams of carboxylic acids having 4 to 8 carbon atoms In general, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid.
• polyamidoamines have primary and secondary NH groups and are soluble in water.
• Ethyleneimine-grafted polyamidoamines can be prepared by allowing ethyleneimine to act on polyamidoamine described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate.
• ethyleneimine is grafted onto the relevant polyamidoamine.
• polyamidoamine per basic nitrogen atom in the polyamidoamine, one can graft 1 to 10 ethyleneimine units, i. H. 100 parts by weight of polyamidoamine are used for about 10 to 500 parts by weight of ethylenimine.
• Preferred alkyleneimine polymer is polyethyleneimine.
• Alkyleneimine polymer is used in the context of the present invention in covalently modified form, specifically in the range from 2 to 80% by weight, preferably from 5 to 60% by weight, of alkylene oxide side chains, based on the total alkoxylated alkyleneimine -Polymer (B).
• alkoxylation can be used epoxides, for example ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin.
• Preferred alkoxylation reagents are ethylene oxide and propylene oxide and mixtures of ethylene oxide and propylene oxide.
• alkoxylated alkyleneimine polymer (B) alkoxylates in the range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer.
• modified polyalkyleneimine (B) is selected from polyethyleneimines reacted with ethylene oxide or propylene oxide.
• Modified polyalkyleneimine (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
• High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol
• low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol
• Examples of low molecular weight organic counterions are acetate, propionate and benzoate.
• Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
• modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g to a maximum of 25 meq / g (milliequivalents / g), preferably to 22 meq / g, where g is relates to modified polyalkyleneimine (B) without consideration of the counterions.
• the cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.
• modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range of 1.1 to 10, preferably 1.5 to 5.
• aminocarboxylate A
• modified polyalkyleneimine B
• formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range from 1000 to 1 to 25 to 1.
• formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexanatri- ummetaphosphat.
• free from in connection with phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
• Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.
• formulations according to the invention contain no further components, which are advantageous, for example, for use in dishwashing and / or kitchen utensils, but can easily be formulated with further components and are therefore suitable as starting material.
• formulations according to the invention contain sodium citrate (C).
• sodium citrate comprises the mono- and preferably the disodium salt with.
• Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
• (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also called “bleaching agent (D)".
• Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, and sodium persulfate, where the term "persulfate” respectively the salt of peracid H2SO5 and the Peroxodisulfate includes.
• the alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.
• formulation according to the invention comprises zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, particularly preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate,
• bleaching agent (D) preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
• formulation according to the invention is solid at room temperature, for example a powder or a tablet.
• formulation of the invention is liquid at room temperature.
• the formulation according to the invention is a granulate, a liquid preparation or a gel.
• the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.
• formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizers.
• surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers
• surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
• Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
• R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
• R 2 selected from Cs-C22-alkyl, for example n-CsH-i, n-doF i, n-Ci2H25, nC-uF s), n-Ci6H33 or n-Ci8H 3 7,
• R 3 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
• neo-pentyl 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl
• m and n are in the range of zero to 300, the sum of n and m being at least one.
• m is in the range of 1 to 100 and n is in the range of 0 to 30.
• Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) where the variables are defined as follows:
• R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,
• R 4 is selected from C 6 -C 20 -alkyl, in particular nC & Hn, n-doF i, n-Ci 2 H 25, nC-uF s), n-Ci6H33, n
• a is a number in the range of 1 to 6,
• b is a number in the range of 4 to 20, is a number in the range of 4 to 25.
• compounds of the general formula (II) may be block copolymers or random copolymers, preferred are block copolymers.
• suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
• suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
• amine oxides or alkyl glycosides are also suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
• 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.
• formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
• Formulations of the invention may contain one or more enzymes.
• enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
• Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
• Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders.
• Suitable builders are silicates, especially sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, ⁇ -Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccina tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.
• builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
• Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
• a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 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 in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
• copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-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 hydrophobically modified monomers 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, such as 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- a-olefins and polyisobutene with an average of 12 to 100 carbon atoms per molecule.
• 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.
• Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
• 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.
• amphoteric polymers can also be used as builders.
• Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder. In one embodiment of the present invention, formulations according to the invention may contain one or more co-builders.
• cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
• hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. 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.
• Formulations of 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 according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
• 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 according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
• Formulations of 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 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 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, for example, N-nonanoylsuccinimide ,, 1, 5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
• MMA salts N-methylmorpholinium acetonitrile salts
• DADHT 1, 5-diacetyl-2,2-dioxo hexahydro-1,3,5-triazine
• nitrile quats trimethylammonium acetonitrile salts
• TAED tetraacetylethylenediamine
• TAED tetraacetylhexylenediamine
• Formulations according to the invention may contain one or more corrosion inhibitors.
• these are understood as meaning compounds which inhibit the corrosion of metal.
• suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
• formulations according to the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.
• Formulations of the invention may contain one or more builders, for example, sodium sulfate.
• Formulations according to the invention may contain one or more defoamers, selected for example from silicone oils and paraffin oils.
• formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
• Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
• kitchen utensils include, for example, pots, pans, casseroles, and also metal objects such as, for example, skimmers, roasting knives and garlic presses.
• a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
• the objects in question may be those that are essentially glassy, such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.
• Glass surface may be decorated, for example colored or printed, or not decorated.
• glass includes any glass, for example lead glass and, in particular, soda lime glass, crystal glass and borosilicate glass, preferably a dishwasher with automatic dishwashing.
• At least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
• water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
• German hardness being taken to mean in particular the calcium hardness.
• rinsing water with a hardness in the range of 1 to 30 ° dH preferably 2 to 25 ° dH can be used.
• machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation according to the invention to clean glass together with metal objects, for example together with pots, pans or garlic presses.
• formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
• a further subject of the present invention is a process for the preparation of formulations according to the invention, in short also called production process according to the invention.
• preparation process according to the invention it is possible, for example, to proceed in such a way that
• a aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
• Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
• one or more other ingredients (E) may be used for the invention.
• mixing appropriate formulation for example with one or more surfactants, one or more enzymes, one or more builders, one or more co-builders, in particular phosphorus-free builder, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more Bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, with buffer or dye.
• the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spraying - granulation or compaction.
• the water is removed, in whole or in part, at a pressure in the range from 0.3 to 2 bar.
• the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
• the cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.
• the water content of liquid formulations can vary from 35 to 90% water.
• modified polyethylenimines B was always determined as follows (see also: Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251): 1 g of the respective modified polyethyleneimine (B) was dissolved in 100 ml of demineralized water. With a buffer solution and aqueous HCl was set to a pH of 4.0, determined potentiometrically. Three ml of an aqueous solution of toluidine blue (50 mg / l water) were added and titrated N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml to a color change of blue to pink. The charge density was calculated as follows:
• LA 0.4 ⁇ KV LA: charge density of the respective modified polyethyleneimine (B), meq / g (milliequivalent / g)
• base mixtures were prepared from the starting materials according to Table 1. The starting materials were mixed dry.
• MGDA methylglycine diacetic acid as trisodium salt
• TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylenediamine
• M w PEI refers to the molecular weight of the polyethylenimine used for the alkoxylation, ie to unmodified polyethyleneimine.
• PEI refers to unmodified polyethyleneimine.
• the glasses were placed in the upper dish rack of the dishwasher.
• the dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 3, where Table 3 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or ( E) and (B) of each formulation according to the invention are specified individually.
• Rinsing was carried out at a rinse temperature of 55 ° C.
• the water hardness was in each case in the range of zero to 2 ° dH.
• the evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
• the weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle. The weight loss is the difference between the two values.
• the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
• Interim scores (e.g., L3-4) were also allowed on the match.
• formulations according to the invention were also always superior to the corresponding comparative formulations in terms of the inhibition of glass corrosion.

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• 2013
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