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
  • C11D3/16—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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
  • 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
  • C11D3/37—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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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

Definitions

• 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 rubbing 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 suggests formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used.
• WO 99/05248 discloses dishwashing compositions comprising polymers of amino group-containing vinyl polymers.
• WO 2009/062699 discloses dishwashing compositions containing MGDA or IDS as complexing agent and percarbonate as bleaching agent.
• Dishwashing agents 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. The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases.
• formulations defined above were found, also called formulations according to the invention.
• inorganic cations such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, in particular triethanol ammonium, N, N-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 such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, in particular triethanol ammonium, N, N-diethanolammonium, N-mono-C 1 -C 4 -alkyl
• 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 (GLDA).
• MGDA methylglycine diacetate
• IDS iminodisuccinic acid
• GLDA glutamic acid diacetate
• MGDA methylglycine diacetate
• IDS iminodisuccinic acid
• GLDA glutamic acid diacetate
• 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.
• polyalkylenepolyamines 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 ,
• Polyalkylenepolyamin and in particular polyethyleneimine can for example have an average molecular weight (M w ) of at least 300 g / mol, preferably the average molecular weight of alkyleneimine polymer in the range of 500 to 1,000,000 g / mol, particularly preferably 800 to 25,000 g / mol, determined by gel permeation chromatography (GPC).
• M w average molecular weight
• Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as the alkyleneimine polymer.
• Suitable quaternizing agents (alkylating agents) are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chloride such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride , If quaternized (alkylated) polyalkylenepolyamines are covalently modified as the alkyleneimine polymer, the degree of quaternization (alkylation) is preferably from 1 to 25, more preferably up to 20 mol%, based on quaternizable (
• Polyalkylenepolyamines and in particular polyethylenimines can furthermore be covalently modified in alkoxylated form in a partially alkoxylated form with C 2 -C 22 -epropoxides as alkyleneimine polymer.
• suitable C 2 -C 22 epoxides are ethylene oxide, propylene oxide, n-hexylene oxide, styrene oxide.
• the degree of alkoxylation is preferably 1 to 25, particularly preferably up to 20 mol%, based on alkoxylatable N atoms in the relevant 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 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 above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
• the aforementioned 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, 0.8 to 1.4 mol of 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.
• per basic nitrogen atom in the polyamidoamine one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.
• Preferred alkyleneimine polymer is polyethyleneimine.
• polyethyleneimine has an average molecular weight M w in the range from 500 to 1,000,000 g / mol, preferably in the range from 600 to 75,000 g / mol, particularly preferably in the range from 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).
• polyethyleneimines are selected from highly branched polyethyleneimines. Highly branched polyethylenimines are characterized by their high degree of branching (DB).
• highly branched polyethyleneimines are polyethyleneimines having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and very particularly preferably at least 0, 5th
• polyethylenimine is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.
• Alkyleneimine polymer is used in the context of the present invention in covalently modified form, in such a way that a total of up to 75 mol%, preferably a total of 5 to 60 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid are reacted.
• the reaction (modification) may therefore be, for example, an alkylation or an amidation.
• Examples of ethylenically unsaturated C 3 -C 10 -carboxylic acids are unsaturated fatty acids and preferably ⁇ , ⁇ -ethylenically unsaturated C 3 -C 10 -carboxylic acids, for example (E) - or (Z) -crotonic acid, methacrylic acid and especially acrylic acid.
• C 3 -C 10 -carboxylic acid (s) C 3 -C 10 -carboxylic acid is / are preferably added in the sense of a Michael addition to nitrogen atoms from NH 2 groups or NH groups from alkyleneimine polymer.
• C 5 -C 12 carboxylic acids which have no ethylenic double bond are valeric acid, caproic acid, caprylic acid, n-octanoic acid, n-decanoic acid and lauric acid.
• a reaction with C 5 -C 12 -carboxylic acid (s) which have no ethylenic double bond For example, an amidation of nitrogen atoms from NH 2 groups or NH groups from alkyleneimine polymer is preferably carried out.
• esters for example the C 1 -C 4 -alkyl esters, in particular the ethyl and the methyl esters.
• carbonic acid derivatives are the di-C 1 -C 2 -alkyl esters of carbonic acid, such as dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate, and in particular cyclic carbonates, such as ethylene carbonate and propylene carbonate. Preferred is ethylene carbonate.
• modified polyalkyleneimine (B) up to a maximum of 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer are reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid, preferably a total of 5 to 60 mol%.
• Tertiary nitrogen atoms in polyalkyleneimine (B) are usually not reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid.
• modified polyalkyleneimine (B) which is obtainable from alkyleneimine polymers and in particular polyethyleneimines (B1) which are reacted with at least one ethylenically unsaturated C 3 -C 10 -carboxylic acid in free form in the formulation according to the invention Acid.
• 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 (milliequivalents / g), preferably 5 to 22 meq / g, with no mention in g of modified polyalkyleneimine (B) relates to the counterions.
• the cationic charge density can be determined, for example, by titration, for example by titration with polyvinyl sulfate.
• Modified polyalkyleneimines (B) may also contain in copolymerized form one or more anionic comonomers, for example (meth) acrylic acid.
• 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.
• modified polyalkyleneimine (B) has a molecular weight Mw in the range of 550 to 1.5 x 10 6 g / mol.
• Contain formulations according to the invention total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of modified polyalkyleneimine (B), preferably 0.05 to 2.5 wt .-%, in each case based on solids content of the relevant formulation.
• formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio of 1000: 1 to 25: 1.
• formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummetaphosphat.
• free from in connection with phosphates and polyphosphates in the context of the present invention is 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 includes 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.
• 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 H 2 SO 5 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 contains zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, more preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate, a total of zero to 15% by weight of 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. in each case based on solids content of the relevant formulation.
• 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.
• the formulation according to the invention is free from those heavy metal compounds which do not function as bleach catalysts, in particular compounds of iron and bismuth.
• “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 Solids content.
• the formulation according to the invention 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 .
• the heavy metals are precious metals and 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.
• 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 tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
• 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.
• Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
• these may be block copolymers or random copolymers, preference being given to 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.
• 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, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , furthermore fatty acid sulfonates , ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.
• builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
• 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 selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -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 are used as listed below.
• Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C 22 - ⁇ -olefin, a mixture of C 20 -C 24 - ⁇ -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 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.
• Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
• 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.
• 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.
• formulations according to the invention may contain one or more co-builders.
• co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
• 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 of the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethyl ammonium acetonitrile salts, N-acylimides such as N-nonanoyl succinimide, "1,5-diacetyl-2,2-dioxohexahydro-1,3 , 5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
• MMA salts N-methylmorpholinium acetonitrile salts
• DADHT 5-triazine
• nitrile quats trimethylammonium acetonitrile salts
• TAED tetraacetylethylenediamine
• TAED tetraacetylhexylenediamine
• Formulations of the invention may contain one or more corrosion inhibitors.
• corrosion inhibitors such compounds that 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, phloroglucin 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 of 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.
• Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils.
• kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters 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 which are essentially glassware 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 glasses.
• Machine cleaning is preferably dishwashing with a dishwasher (English: 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.
• 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 of the present invention to clean glass together with metal objects, such as 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.
• Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
• one or more surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders a plurality of co-builders, in particular phosphorus-free builders, 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 Buffer or dye.
• one or more surfactants for
• 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, spray granulation or compaction ,
• the water is removed, in whole or in part, at a pressure in the range of 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 dosing units, packaged or unpackaged.
• the water content of liquid formulations can vary from 35 to 90% water.
• Base mixtures were prepared from the starting materials according to Table 1. The starting materials were mixed dry.
• Table 1 Basic mixtures for experiments with formulations according to the invention and comparative formulations Base 1
• Base 2 Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC 18 H 37 (OCH 2 CH 2 ) 9 OH 5 5
• 10 10
• Sodium percarbonate (D.1) 10.5 10.5 10.5 TAED 4 4 4 Na 2 CO 3 19.5 19.5 19.5
• Modified polyethylenimines (B) according to Table 2 were used: Table 2: Modified polyethyleneimines abbreviation M w (g / mol) Modification with Functionalization (mol%) Cationic charge density (meq / g) B.1.1.1 800 acrylic acid 5 15 B.1.1.2 800 acrylic acid 20 11 B.1.1.3 800 acrylic acid 40 7 B.1.2.1 2000 acrylic acid 15 12 B.1.3.1 5000 acrylic acid 15 13 B.1.4.1 50,000 acrylic acid 15 11.5 B.2.1.1 800 AmeisenTexitril 20 12 B.2.2.2 2000 Ameisenklarenitril 15 11 B.2.3.3 5000 AmeisenLiterenitril 25 9 B.2.4.4 50,000 Ameisenklaitril 10 14 B.3.1.1 800 valeric 10 16 B.3.2.2 2000 valeric 40 9 B.3.3.3 5000 valeric 15 14 B.4.1.1 800 lauric acid 5 18 B.4.1.2 800 lauric acid 15 14.5 B.4.2.3 2000 lauric acid 20 12.5 B.4.
• the molecular weight M w was determined on the underlying polyethyleneimines, so each prior to modification.
• the functionalization refers to the sum of the primary and secondary N atoms in the respective polyethyleneimine.
• Dishwasher Miele G 1222 SCL Program: 65 ° C (with pre-rinse) ware: 3 champagne glasses “GILDE”, 3 shot glasses, "INTERMEZZO"
• 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 2, where Table 2 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or ( E) and (B) of inventive formulation individually specified.
• 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 specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid, to remove any impurities.
• the test pieces were dried, their weight determined and fixed on the grid floor insert.
• 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).
• Base mixture [g] (A.1) [g] (B) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating shot glass V-1
• Base 3:17 3 24 (B.5.1.1) 9 6 L4, T5 L4-5, T5 4 Base 1:17 3 24 (B.5.1.2) 16 12 L4, T4-5 L4, T4-5 5

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• 2013
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