EP2841548B1 - Formulations, use of same as or for manufacture of dish-washing agents and their manufacture - Google Patents
Formulations, use of same as or for manufacture of dish-washing agents and their manufacture Download PDFInfo
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- EP2841548B1 EP2841548B1 EP13717782.0A EP13717782A EP2841548B1 EP 2841548 B1 EP2841548 B1 EP 2841548B1 EP 13717782 A EP13717782 A EP 13717782A EP 2841548 B1 EP2841548 B1 EP 2841548B1
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- carboxylic acid
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
Description
Die vorliegende Erfindung betrifft Formulierungen, enthaltend
- (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens ein Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
- (B) insgesamt im Bereich von 0,001 bis 5 Gew.-% mindestens ein Alkylenimin-Polymer, das mit mindestens einer Carbonsäure oder mindestens einem Derivat einer Carbonsäure oder mindestens einem Derivat von Kohlensäure kovalent modifiziert ist, wobei bis maximal 75 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers mit Carbonsäure bzw. Derivat von Carbonsäure bzw. Kohlensäure oder mit Blausäure und Formaldehyd umgesetzt sind, bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.
- (A) in total in the range of 1 to 50% by weight of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
- (B) in total in the range of 0.001 to 5 wt .-% of at least one alkyleneimine polymer which is covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid, wherein up to 75 mol% of 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 or with hydrocyanic acid and formaldehyde, based in each case on the solids content of the relevant formulation.
Weiterhin betrifft die vorliegende Erfindung ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen und ihre Verwendung als oder zur Herstellung von Geschirrspülmitteln, insbesondere von Geschirrspülmitteln für das maschinelle Geschirrspülen.Furthermore, 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.
Geschirrspülmittel haben vielerlei Anforderungen zu erfüllen. So haben sie das Geschirr gründlich zu reinigen, sie sollen im Abwasser keine schädlichen oder potenziell schädlichen Substanzen aufweisen, sie sollen das Ablaufen und Trocknen des Wassers vom Geschirr gestatten, und sie sollen beim Betrieb der Spülmaschine nicht zu Problemen führen. Schließlich sollen sie nicht zu ästhetisch unerwünschten Folgen am zu reinigenden Gut führen. Besonders ist in diesem Zusammenhang die Glaskorrosion zu nennen.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.
Glaskorrosion kommt nicht nur durch mechanische Effekte zustande, beispielsweise durch Aneinanderreiben von Gläsern oder mechanischen Kontakt der Gläser mit Teilen der Spülmaschine, sondern wird hauptsächlich durch chemische Einflüsse gefördert. Beispielsweise können bestimmte Ionen durch wiederholtes maschinelles Reinigen aus dem Glas gelöst werden, was die optischen und somit die ästhetischen Eigenschaften nachteilig verändert.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. For example, certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
Bei der Glaskorrosion beobachtet man mehrere Effekte. Zum einen kann man die Bildung von mikroskopisch feinen Rissen beobachten, die sich in Form von Linien bemerkbar machen. Zum anderen kann man in vielen Fällen eine generelle Eintrübung beobachten, beispielsweise eine Aufrauhung, die das betreffende Glas unästhetisch aussehen lassen. Derartige Effekte werden insgesamt auch unterteilt in irisierende Verfärbung, Riefenbildung sowie flächen- und ringförmige Trübungen.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.
Aus
Aus
Es bestand also die Aufgabe, Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden und die Glaskorrosion inhibieren oder zumindest besonders gut verringern. Es bestand weiterhin die Aufgabe, ein Verfahren zur Herstellung von Formulierungen bereit zu stellen, die als oder zur Herstellung von Geschirrspülmitteln geeignet sind und die die aus dem Stand der Technik bekannten Nachteile vermeiden. Es bestand weiterhin die Aufgabe, Verwendungen von Formulierungen bereit zu stellen.It was therefore the object to provide formulations which are suitable as or for the production of dishwashing agents and which avoid the disadvantages known from the prior art and inhibit glass corrosion or at least reduce it particularly well. A further object was to provide a process for the preparation of formulations which are suitable as or for the production of dishwasher detergents and which avoid the disadvantages known from the prior art. It was also the task to provide uses of formulations.
Dementsprechend wurden die eingangs definierten Formulierungen gefunden, kurz auch erfindungsgemäße Formulierungen genannt.Accordingly, the formulations defined above were found, also called formulations according to the invention.
Erfindungsgemäße Formulierungen enthalten
- (A) insgesamt im Bereich von 1 bis 50 Gew.-% mindestens ein Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, im Rahmen der vorliegenden Erfindung kurz auch Aminocarboxylat (A) oder auch Verbindung (A) genannt.
- (A) in total in the range of 1 to 50 wt .-% of at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, in the context of the present invention also briefly aminocarboxylate (A) or also called compound (A).
Bevorzugt wählt man Verbindung (A) als freie Säure, besonders bevorzugt in partiell oder vollständig neutralisierter Form, also als Salz. Als Gegenionen kommen beispielsweise anorganische Kationen, beispielsweise Ammonium, Alkali oder Erdalkali in Frage, bevorzugt Mg2+, Ca2+, Na+, K+, oder organische Kationen, bevorzugt mit einem oder mehreren organischen Resten substituiertes Ammonium, insbesondere Triethanolammonium, N,N-Diethanolammonium, N-Mono-C1-C4-alkyldiethanolammonium, beispielsweise N-Methyl-diethanolammonium oder N-n-Butyldiethanolammonium, und N,N-Di-C1-C4-alkylethanolammonium.Preference is given to choosing compound (A) as the free acid, particularly preferably in partially or completely neutralized form, ie as salt. As counterions, for example 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.
Ganz besonders bevorzugte Verbindungen (A) sind die Alkalimetallsalze, insbesondere die Natriumsalze von Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA).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).
Ganz besonders bevorzugt ist Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) bzw. Glutaminsäurediacetat (GLDA) vollständig neutralisiert.Very particular preference is given to fully neutralizing methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) or glutamic acid diacetate (GLDA).
Erfindungsgemäße Formulierungen enthalten weiterhin
- (B) insgesamt im Bereich von 0,001 bis 5 Gew.-% mindestens ein Alkylenimin-Polymer, das mit mindestens einer Carbonsäure oder mindestens einem Derivat einer Carbonsäure oder mindestens einem Derivat von Kohlensäure kovalent modifiziert ist, kurz auch modifiziertes Polyalkylenimin (B) genannt, wobei bis maximal 75 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers mit Carbonsäure bzw. Derivat von Carbonsäure bzw. Kohlensäure oder mit Blausäure und Formaldehyd umgesetzt sind.
- (B) at least in the range from 0.001 to 5 wt .-% of at least one alkyleneimine polymer which is covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid, also referred to as modified polyalkyleneimine (B), wherein up to 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 or with hydrocyanic acid and formaldehyde.
Unter Alkylenimin-Polymeren sind im Rahmen der vorliegenden Erfindung solche polymere Materialien zu verstehen, die durch Homo- oder Copolymerisation von einem bzw. mehreren cyclischen Iminen erhalten werden, oder durch Pfropfung eines (Co)polymers mit mindestens einem cyclischen Imin. Beispiele sind Polyalkylenpolyamine und mit Ethylenimin gepfropften Polyamidoamine.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.
Unter Polyalkylenpolyaminen sollen im Rahmen der vorliegenden Erfindung vorzugsweise solche Polymere verstanden werden, die mindestens sechs Stickstoffatome und mindestens fünf C2-C10-Alkyleneinheiten, bevorzugt C2-C3-Alkylen-einheiten pro Molekül enthalten, zum Beispiel Pentaethylenhexamin, und insbesondere Polyethylenimine.For the purposes of the present invention, 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 ,
Polyalkylenpolyamin und insbesondere Polyethylenimin kann beispielsweise ein mittleres Molekulargewicht (Mw) von mindestens 300 g/mol haben, bevorzugt liegt das mittlere Molekulargewicht von Alkylenimin-Polymer im Bereich von 500 bis 1.000.000g/mol, besonders bevorzugt 800 bis 25.000 g/mol, ermittelt durch Gelpermeationschromatographie (GPC).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).
Polyalkylenpolyamine können in teilweise quaternierter (alkylierter) Form als Alkylenimin-Polymer kovalent modifiziert werden. Geeignete Quaternierungsmittel (Alkylierungsmittel) sind zum Beispiel Alkylhalogenide, insbesondere C1-C10-Alkylchlorid wie Methylchlorid, Methylbromid, Methyliodid, Ethylchlorid, Ethylbromid, n-Butylchlorid, tert.-Butylchlorid, n-Hexylchlorid, weiterhin Epichlorhydrin, Dimethylsulfat, Diethylsulfat und Benzylchlorid. Falls quaternierte (alkylierte) Polyalkylenpolyamine als Alkylenimin-Polymer kovalent modifiziert werden, beträgt der Grad der Quaternierung (alkylierung) bevorzugt 1 bis 25, besonders bevorzugt bis zu 20 mol-%, bezogen auf quaternierbare (alkylierbare) N-Atome in Alkylenimin-Polymer.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 (alkylatable) N atoms in the alkyleneimine polymer.
Polyalkylenpolyamine und insbesondere Polyethylenimine können des Weiteren in partiell mit C2-C22-Epoxiden alkoxylierter Form als Alkylenimin-Polymer kovalent modifiziert sein. Beispiele für geeignete C2-C22-Epoxide sind Ethylenoxid, Propylenoxid, n-Hexylenoxid, Styroloxid. Falls teilweise mit C2-C22-Epoxiden alkoxylierte Polyalkylenpolyamine als Alkylenimin-Polymer kovalent modifiziert werden, beträgt der Grad der Alkoxylierung bevorzugt 1 bis 25, besonders bevorzugt bis zu 20 mol-%, bezogen auf alkoxylierbare N-Atome im betreffenden Alkylenimin-Polymer.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. Examples of suitable C 2 -C 22 epoxides are ethylene oxide, propylene oxide, n-hexylene oxide, styrene oxide. If partially alkoxylated with C 2 -C 22 epoxides polyalkylenepolyamines are covalently modified as alkyleneimine polymer, 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 ,
Weiterhin sind mit Ethylenimin gepfropften Polyamidoamine als Alkylenimin-Polymere geeignet. Geeignete Polyamidoamine sind zum Beispiel durch Umsetzung von C4-C10-Dicarbonsäuren mit Polyalkylenpolyaminen erhältlich, die vorzugsweise 3 bis 10 basische Stickstoffatome im Molekül enthalten. Geeignete Dicarbonsäuren sind beispielsweise Bernsteinsäure, Maleinsäure, Adipinsäure, Glutarsäure, Korksäure, Sebacinsäure oder Terephthalsäure. Man kann auch Mischungen von vorstehend genannten Dicarbonsäuren einsetzen, zum Beispiel Mischungen von Adipinsäure und Glutarsäure oder Mischungen von Maleinsäure und Adipinsäure. Bevorzugt setzt man Adipinsäure zur Herstellung von Polyamidoaminen ein. Geeignete Polyalkylenpolyamine, die mit vorstehend genannten Dicarbonsäuren kondensiert werden, sind zum Beispiel Diethylentriamin, Triethylentetramin, Dipropylentriamin, Tripropylentetramin, Dihexamethylentriamin, Aminopropylethylendiamin und bis-Aminopropyl-ethylen-diamin. Vorstehend genannte Polyalkylenpolyamine können auch in Form von Mischungen bei der Herstellung von Polyamidoamin eingesetzt werden. Die Herstellung von Polyamidoamin erfolgt vorzugsweise in Substanz, kann jedoch auch gegebenenfalls in inerten Lösungsmitteln vorgenommen werden. Die Kondensation von Dicarbonsäure mit Polyalkylenpolyamin erfolgt bei höheren Temperaturen, zum Beispiel im Bereich von 120 bis 220 °C. Das während der Reaktion gebildete Wasser wird aus dem Reaktionsgemisch abdestilliert. Die Kondensation kann gegebenenfalls in Gegenwart von Lactonen oder Lactamen von Carbonsäuren mit 4 bis 8 Kohlenstoffatomen vorgenommen werden. Pro Mol Dicarbonsäure verwendet man im Allgemeinen 0,8 bis 1,4 mol Polyalkylenpolyamin. So erhältliche Polyamidoamine weisen primäre und sekundäre NH-Gruppen auf und sind in Wasser löslich.Furthermore, 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. Examples of 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. In general, 0.8 to 1.4 mol of polyalkylenepolyamine are used per mole of dicarboxylic acid. Thus obtainable polyamidoamines have primary and secondary NH groups and are soluble in water.
Mit Ethylenimin gepfropfte Polyamidoamine sind dadurch herstellbar, dass man Ethylenimin in Gegenwart von Brönstedt-Säuren oder Lewis-Säuren, zum Beispiel Schwefelsäure, Phosphorsäure oder Bortrifluoridetherat, auf oben beschriebenes Polyamidoamin einwirken lässt. Dadurch wird Ethylenimin auf das betreffende Polyamidoamin aufgepfropft. Zum Beispiel kann man pro basischem Stickstoffatom im Polyamidoamin 1 bis 10 Ethylenimineinheiten aufpfropfen, d. h. auf 100 Gewichtsteile Polyamidoamin setzt man etwa 10 bis 500 Gewichtsteile Ethylenimin ein.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. As a result, ethyleneimine is grafted onto the relevant polyamidoamine. For example, 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.
Bevorzugte Alkylenimin-Polymer ist Polyethylenimin.Preferred alkyleneimine polymer is polyethyleneimine.
In einer Ausführungsform der vorliegenden Erfindung weist Polyethylenimin ein mittleres Molekulargewicht Mw im Bereich von 500 bis 1.000.000 g/mol auf, bevorzugt im Bereich von 600 bis 75.000 g/mol, besonders bevorzugt im Bereich von 800 bis 25.000 g/mol, bestimmbar beispielsweise durch Gelpermeationschromatographie (GPC).
In einer Ausführungsform der vorliegenden Erfindung wählt man Polyethylenimine aus hochverzweigten Polyethyleniminen. Hochverzweigte Polyethylenimine werden durch ihren hohen Verzweigungsgrad (Degree of Branching, DB) charakterisiert. Der Verzweigungsgrad lässt sich beispielsweise durch 13C-NMR-Spektroskopie, vorzugsweise in D2O, bestimmen und ist wie folgt definiert:
In one embodiment of the present invention, polyethyleneimines are selected from highly branched polyethyleneimines. Highly branched polyethylenimines are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by 13 C-NMR spectroscopy, preferably in D 2 O, and is defined as follows:
Als hochverzweigte Polyethylenimine gelten im Rahmen der vorliegen Erfindung Polyethylenimine mit DB im Bereich von 0,1 bis 0,95, bevorzugt 0,25 bis 0,90 besonders bevorzugt im Bereich von 0,30 bis 0,80 und ganz besonders bevorzugt mindestens 0,5.In the context of the present invention, 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
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Polyethylenimin um hochverzweigte Polyethylenimine (Homopolymere) mit einem mittleren Molekulargewicht Mw im Bereich von 600 bis 75.000 g/mol, bevorzugt im Bereich von 800 bis 25.000 g/mol.In one embodiment of the present invention, 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.
Alkylenimin-Polymer wird im Rahmen der vorliegenden Erfindung in kovalent modifizierter Form eingesetzt, und zwar so, dass insgesamt bis maximal 75 mol-%, bevorzugt insgesamt 5 bis 60 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers mit mindestens einer Carbonsäure oder mindestens einem Derivat einer Carbonsäure oder mindestens einem Derivat von Kohlensäure umgesetzt sind. Bei der Umsetzung (Modifizierung) im Sinne der vorliegenden Anmeldung kann es sich also beispielsweise um eine Alkylierung oder eine Amidierung handeln.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. In the context of the present application, the reaction (modification) may therefore be, for example, an alkylation or an amidation.
In einer Ausführungsform der vorliegenden Erfindung man wählt man modifiziertes Polyalkylenimin (B) aus Alkylenimin-Polymeren und insbesondere Polyethyleniminen,
- (B1) die umgesetzt sind mit mindestens einer ethylenisch ungesättigten C3-C10-Carbonsäure oder
- (B2) die umgesetzt sind mit mindestens einer C5-C12-Carbonsäure, die keine ethylenische Doppelbindung aufweist,
- (B3) die umgesetzt sind mit mindestens einem Kohlensäureester und
- (B4) die umgesetzt sind mit Blausäure und Formaldehyd, beispielsweise im Sinne einer Streckersynthese.
- (B1) which are reacted with at least one ethylenically unsaturated C 3 -C 10 carboxylic acid or
- (B2) which are reacted with at least one C 5 -C 12 -carboxylic acid which has no ethylenic double bond,
- (B3) which are reacted with at least one carbonic acid ester and
- (B4) which are reacted with hydrocyanic acid and formaldehyde, for example in the sense of a Strecker synthesis.
Beispiele für ethylenisch ungesättigte C3-C10-Carbonsäuren sind ungesättigte Fettsäuren und vorzugsweise α,β-ethylenisch ungesättigte C3-C10-Carbonsäuren, beispielsweise (E)- oder (Z)-Crotonsäure, Methacrylsäure und insbesondere Acrylsäure. Durch eine Umsetzung mit C3-C10-Carbonsäure(n) wird/werden C3-C10-Carbonsäure vorzugsweise im Sinne einer Michael-Addition an Stickstoffatome aus NH2-Gruppen oder NH-Gruppen aus Alkylenimin-Polymer addiert.Examples of ethylenically unsaturated C 3 -C 10 -carboxylic acids are unsaturated fatty acids and preferably α, β-ethylenically unsaturated C 3 -C 10 -carboxylic acids, for example (E) - or (Z) -crotonic acid, methacrylic acid and especially acrylic acid. By reaction with 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.
Beispiele für C5-C12-Carbonsäure, die keine ethylenische Doppelbindung aufweisen, sind Valeriansäure, Capronsäure, Caprylsäure, n-Oktansäure, n-Dekansäure und Laurinsäure. Durch eine Umsetzung mit C5-C12-Carbonsäure(n), die keine ethylenische Doppelbindung aufweisen, wird vorzugsweise eine Amidierung von Stickstoffatomen aus NH2-Gruppen oder NH-Gruppen aus Alkylenimin-Polymer ausgeführt.Examples of 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. By 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.
Beispiele für Derivate von C5-C12-Carbonsäuren, die keine ethylenische Doppelbindung aufweisen, sind deren Ester, beispielsweise die C1-C4-Alkylester, insbesondere die Ethyl- und die Methylester. Zu nennen sind Valeriansäuremethylester, Capronsäuremethylester, Caprylsäuremethylester, n-Oktansäuremethylester, n-Dekansäuremethylester, Valeriansäureethylester, Capronsäureethylester, Caprylsäureethylester, n-Oktansäureethylester und n-Dekansäureethylester.Examples of derivatives of C 5 -C 12 -carboxylic acids which have no ethylenic double bond are their esters, for example the C 1 -C 4 -alkyl esters, in particular the ethyl and the methyl esters. Mention may be made of methyl valerate, methyl caprone, methyl caprylate, methyl n-octanoate, methyl n-decanoate, ethyl valerate, ethyl caprylate, ethyl caprylate, ethyl n-octanoate and ethyl n-decanoate.
Beispiele für Kohlensäurederivate sind die Di-C1-C2-Alkylester der Kohlensäure wie Dimethylcarbonat, Diethylcarbonat und Ethylmethylcarbonat, und insbesondere cyclische Carbonate wie Ethylencarbonat und Propylencarbonat. Bevorzugt ist Ethylencarbonat.Examples of 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.
Dabei sind in modifiziertem Polyalkylenimin (B) bis insgesamt maximal 75 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers mit Carbonsäure bzw. Derivat von Carbonsäure bzw. Kohlensäure umgesetzt, bevorzugt insgesamt 5 bis 60 mol-%.In 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%.
Tertiäre Stickstoffatome in Polyalkylenimin (B) sind in der Regel nicht mit Carbonsäure bzw. Derivat von Carbonsäure bzw. Kohlensäure umgesetzt.Tertiary nitrogen atoms in polyalkyleneimine (B) are usually not reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid.
In einer anderen Ausführungsform der vorliegenden Erfindung setzt man modifiziertes Polyalkylenimin (B), das erhältlich ist aus Alkylenimin-Polymeren und insbesondere Polyethyleniminen (B1), die umgesetzt sind mit mindestens einer ethylenisch ungesättigten C3-C10-Carbonsäure, in erfindungsgemäßer Formulierung als freie Säure ein.In another embodiment of the present invention, 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.
Modifiziertes Polyalkylenimin (B) kann als Gegenionen hochmolekulare oder niedermolekulare Anionen aufweisen, organisch oder bevorzugt anorganisch. Hochmolekulare Anionen im Rahmen der vorliegenden Erfindung haben ein mittleres Molekulargewicht von 200 g/mol oder mehr, beispielsweise bis zu 2500 g/mol, niedermolekulare Anionen haben ein Molekulargewicht von weniger als 200 g/mol, beispielsweise von 17 bis 150 g/mol. Beispiele für niedermolekulare organische Gegenionen sind Acetat, Propionat und Benzoat. Beispiele für niedermolekulare anorganische Gegenionen sind Sulfat, Chlorid, Bromid, Hydroxid, Carbonat, Methansulfonat und Hydrogencarbonat.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.
In einer Ausführungsform der vorliegenden Erfindung weist modifiziertes Polyalkylenim (B) eine kationische Ladungsdichte von mindestens 5 meq/g (Milliäquivalente/g) auf, bevorzugt 5 bis 22 meq/g, wobei sich die Angabe in g auf modifiziertes Polyalkylenimin (B) ohne Berücksichtigung der Gegenionen bezieht. Die kationische Ladungsdichte kann man beispielsweise durch Titration ermitteln, beispielsweise durch Titration mit Polyvinylsulfat.In one embodiment of the present invention, 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.
Modifizierte Polyalkylenimine (B) können auch ein oder mehrere anionische Comonomere einpolymerisiert enthalten, beispielsweise (Meth)acrylsäure. Kationische Copolymere (B), die auch ein oder mehrere anionischen Comonomere ein polymerisiert enthalten, weisen jedoch mehr kationische als anionische Ladungen pro Molekül auf.Modified polyalkyleneimines (B) may also contain in copolymerized form one or more anionic comonomers, for example (meth) acrylic acid. Cationic copolymers (B), which also contain one or more anionic comonomers polymerized, have more cationic than anionic charges per molecule.
In einer Ausführungsform der vorliegenden Erfindung weist modifiziertes Polyalkylenim (B) eine Molekulargewichtsverteilung Mw/Mn im Bereich von 1,1 bis 10 auf, bevorzugt 1,5 bis 5.In one embodiment of the present invention, 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.
In einer Ausführungsform der vorliegenden Erfindung weist modifiziertes Polyalkylenimin (B) ein Molekulargewicht Mw im Bereich von 550 bis 1,5·106 g/mol auf.In one embodiment of the present invention, modified polyalkyleneimine (B) has a molecular weight Mw in the range of 550 to 1.5 x 10 6 g / mol.
Erfindungsgemäße Formulierungen enthalten
insgesamt im Bereich von 1 bis 50 Gew.-% Aminocarboxylat (A), bevorzugt 10 bis 25 Gew.-%, insgesamt im Bereich von 0,001 bis 5 Gew.-% modifiziertes Polyalkylenimin (B), bevorzugt 0,05 bis 2,5 Gew.-%,
bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.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.
In einer Variante der vorliegenden Erfindung enthält erfindungsgemäße Formulierung Verbindung (A) und modifiziertes Polyalkylenimin (B) in einem Gewichtsverhältnis von 1000 zu 1 bis 25 zu 1.In a variant of the present invention, formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio of 1000: 1 to 25: 1.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von Phosphaten und Polyphosphaten, wobei Hydrogenphosphate mit subsumiert sind, beispielsweise frei von Trinatriumphosphat, Pentanatriumtripolyphosphat und Hexanatriummetaphosphat. Unter "frei von" soll im Zusammenhang mit Phosphaten und Polyphosphaten im Rahmen der vorliegende Erfindung verstanden werden, dass der Gehalt an Phosphat und Polyphosphat in Summe im Bereich von 10 ppm bis 0,2 Gew.-% liegt, bestimmt durch Gravimetrie.In a preferred embodiment of the present invention 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. The term "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.
Erfindungsgemäße Formulierungen können weitere Komponenten enthalten, die beispielsweise für die Verwendung beim Spülen von Geschirr und/oder Küchenutensilien vorteilhaft sind.Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.
In einer anderen Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen keine weiteren Komponenten, die beispielsweise für die Verwendung beim Spülen von Geschirr und/oder Küchenutensilien vorteilhaft sind, können aber leicht mit weiteren Komponenten formuliert werden und eignen sich daher als Ausgangsmaterial.In another embodiment of the present invention 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.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen Natriumcitrat (C). Dabei umfasst der Begriff Natriumcitrat das Mono- und bevorzugt das Dinatriumsalz mit. Natriumcitrat kann als wasserfreies Salz oder als Hydrat, beispielsweise als Dihydrat eingesetzt werden.In one embodiment of the present invention formulations according to the invention contain sodium citrate (C). The term 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.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen
- (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat, im Rahmen der vorliegenden Erfindung auch "Bleichmittel (D)" genannt.
- (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)".
Bevorzugte Bleichmittel (D) sind gewählt aus Natriumperborat, wasserfrei oder beispielsweise als Monohydrat oder als Tetrahydrat oder so genanntes Dihydrat, Natriumpercarbonat, wasserfrei oder beispielsweise als Monohydrat, und Natriumpersulfat, wobei der Begriff "Persulfat" jeweils das Salz der Persäure H2SO5 sowie das Peroxodisulfat mit umfasst.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.
Dabei kann es sich bei den Alkalimetallsalzen jeweils auch um Alkalimetallhydrogencarbonat, Alkalimetallhydrogenperborat und Alkalimetallhydrogenpersulfat handeln. Bevorzugt sind jedoch jeweils die Dialkalimetallsalze.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.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung null bis 50 Gew.-% Natriumcitrat (C), bevorzugt 1 bis 30 Gew.-%, besonders bevorzugt mindestens 5 Gew.-% Natriumcitrat (C), bestimmt als wasserfreies Natriumcitrat,
insgesamt null bis 15 Gew.-% Bleichmittel (D), bevorzugt mindestens 0,5 Gew.-% Bleichmittel (D), gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat. bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.In one embodiment of the present invention 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.
In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung bei Zimmertemperatur fest, beispielsweise ein Pulver oder eine Tablette. In einer anderen Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung bei Zimmertemperatur flüssig. In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung ein Granulat, eine Flüssigzubereitung oder ein Gel.In one embodiment of the present invention, formulation according to the invention is solid at room temperature, for example a powder or a tablet. In another embodiment of the present invention, formulation of the invention is liquid at room temperature. In one embodiment of the present invention, the formulation according to the invention is a granulate, a liquid preparation or a gel.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung 0,1 bis 10 Gew.-% Wasser, bezogen auf die Summe aller Feststoffe der betreffenden Formulierung.In one embodiment of the present invention, 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.
In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von solchen Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, insbesondere von Verbindungen des Eisens und des Wismut. Unter "frei von" soll im Zusammenhang mit Schwermetallverbindungen im Rahmen der vorliegenden Erfindung verstanden werden, dass der Gehalt an Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, in Summe im Bereich von 0 bis 100 ppm liegt, bestimmt nach der Leach-Methode und bezogen auf den Feststoffgehalt. Vorzugsweise weist erfindungsgemäße Formulierung einen Schwermetallgehalt unter 0,05 ppm auf, bezogen auf den Feststoffgehalt der betreffenden Formulierung.In one embodiment of the present invention, 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. 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 Solids content. Preferably, the formulation according to the invention has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.
Als "Schwermetalle" gelten im Rahmen der vorliegenden Erfindung alle Metalle mit einer spezifischen Dichte von mindestens 6 g/cm3. Insbesondere gelten als Schwermetalle Edelmetalle sowie Zink, Wismut, Eisen, Kupfer, Blei, Zinn, Nickel, Cadmium und Chrom.In the context of the present invention, "heavy metals" are all metals having a specific density of at least 6 g / cm 3 . In particular, the heavy metals are precious metals and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
Vorzugsweise enthält erfindungsgemäße Formulierung keine messbaren Anteile an Zink- und Wismutverbindungen, also beispielsweise weniger als 1 ppm.Preferably, formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm.
In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung weitere Inhaltsstoffe (E) aufweisen, beispielsweise ein oder mehrere Tenside, ein oder mehrere Enzyme, einen oder mehrere Builder, insbesondere Phosphor-freie Builder, einen oder mehrere Cobuilder, einen oder mehrere Alkaliträger, ein oder mehrere Bleichmittel, einen oder mehrere Bleichkatalysatoren, einen oder mehrere Bleichaktivatoren, einen oder mehrere Bleichmittelstabilisatoren, einen oder mehrere Entschäumer, einen oder mehrere Korrosionsinhibitoren, einen oder mehrere Gerüststoffe, Puffer, Farbstoffe, einen oder mehrere Duftstoffe, ein oder mehrere organische Lösungsmittel, ein oder mehrere Tablettierhilfsmittel, ein oder mehrere Disintegrationsmittel, einen oder mehrere Verdicker, oder einen oder mehrere Löslichkeitsvermittler.In one embodiment of the present invention, 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.
Beispiele für Tenside sind insbesondere nicht-ionische Tenside sowie Mischungen von anionischen oder zwitterionischen Tensiden mit nicht-ionischen Tensiden. Bevorzugte nicht-ionische Tenside sind alkoxylierte Alkohole und alkoxylierte Fettalkohole, Di- und Multiblockcopolymerisate von Ethylenoxid und Propylenoxid und Umsetzungsprodukte von Sorbitan mit Ethylenoxid oder Propylenoxid, Alkylglycoside und sogenannte Aminoxide.Examples of 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.
Bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (I)
- R1
- gleich oder verschieden und gewählt aus linearem C1-C10-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,
- R2
- gewählt aus C8-C22-Alkyl, beispielsweise n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 oder n-C18H37,
- R3
- gewählt aus C1-C10-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso-Decyl,
- R 1
- identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl,
- R 2
- selected from C 8 -C 22 -alkyl, for example nC 8 H 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 or nC 18 H 37 ,
- R 3
- selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,
Dabei kann es sich bei Verbindungen der allgemeinen Formel (I) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind beispielsweise Verbindungen der allgemeinen Formel (II)
- R1
- gleich oder verschieden und gewählt aus linearem C1-C10-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,
- R4
- gewählt aus C6-C20-Alkyl, insbesondere n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37.
- a
- eine Zahl im Bereich von 1 bis 6,
- b
- ist eine Zahl im Bereich von 4 bis 20,
- d
- ist eine Zahl im Bereich von 4 bis 25.
- R 1
- identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl,
- R 4
- selected from C 6 -C 20 -alkyl, in particular nC 8 H 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 , nC 18 H 37 .
- a
- a number in the range of 1 to 6,
- b
- is a number in the range of 4 to 20,
- d
- is a number in the range of 4 to 25.
Dabei kann es sich bei Verbindungen der allgemeinen Formel (II) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.In the case of compounds of the general formula (II), these may be block copolymers or random copolymers, preference being given to block copolymers.
Weitere geeignete nicht-ionische Tenside sind gewählt aus Di- und Multiblockcopolymeren, aufgebaut aus Ethylenoxid und Propylenoxid. Weitere geeignete nicht-ionische Tenside sind gewählt aus ethoxylierten oder propoxylierten Sorbitanestern. Ebenfalls eignen sich Aminoxide oder Alkylglycoside. Eine Übersicht geeigneter weiterer nichtionischer Tenside findet man in
Es können auch Gemische mehrerer verschiedener nicht-ionischer Tenside enthalten sein.It may also contain mixtures of several different nonionic surfactants.
Beispiele für anionische Tenside sind C8-C20-Alkylsulfate, C8-C20-Alkylsulfonate und C8-C20-Alkylethersulfate mit einer bis 6 Ethylenoxideinheiten pro Molekül.Examples of anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung im Bereich von 3 bis 20 Gew.-% Tensid enthalten.In one embodiment of the present invention, formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
Erfindungsgemäße Formulierungen können ein oder mehrere Enzyme enthalten. Beispiele für Enzyme sind Lipasen, Hydrolasen, Amylasen, Proteasen, Cellulasen, Esterasen, Pectinasen, Lactasen und Peroxidasen.Formulations of the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
Erfindungsgemäße Formulierungen können beispielsweise bis 5 Gew.-% Enzym enthalten, bevorzugt sind 0,1 bis 3 Gew.-%, jeweils bezogen auf gesamten Feststoffgehalt der erfindungsgemäßen Formulierung.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.
Erfindungsgemäße Formulierungen können über Natriumcitrat (C) hinaus einen oder mehrere Builder, insbesondere Phosphat-freie Builder, enthalten. Beispiele für geeignete Builder sind Silikate, insbesondere Natriumdisilikat und Natriummetasilikat, Zeolithe, Schichtsilikate, insbesondere solche der Formel α-Na2Si2O5, β-Na2Si2O5, und δ-Na2Si2O5, weiterhin Fettsäuresulfonate, α-Hydroxypropionsäure, Alkalimalonate, Fettsäuresulfonate, Alkyl- und Alkenyldisuccinate, Weinsäurediacetat, Weinsäuremonoacetat, oxidierte Stärke, und polymere Builder, beispielsweise Polycarboxylate und Polyasparaginsäure.Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula α-Na 2 Si 2 O 5 , β-Na 2 Si 2 O 5 , and δ-Na 2 Si 2 O 5 , furthermore fatty acid sulfonates , α-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.
In einer Ausführungsform der vorliegenden Erfindung wählt man Builder aus Polycarboxylaten, beispielsweise Alkalimetallsalze von (Meth)acrylsäurehomo- oder (Meth)acrylsäurecopolymeren.In one embodiment of the present invention, builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
Als Comonomere eignen sich monoethylenisch ungesättigte Dicarbonsäuren wie Maleinsäure, Fumarsäure, Maleinsäureanhydrid, Itaconsäure und Citraconsäure. Ein geeignetes Polymer ist insbesondere Polyacrylsäure, die bevorzugt ein mittleres Molekulargewicht Mw im Bereich von 2000 bis 40.000 g/mol aufweist, bevorzugt 2.000 bis 10.000 g/mol, insbesondere 3.000 bis 8.000 g/mol. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure und/oder Fumarsäure.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. Also suitable are 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.
Es können auch Copolymere aus mindestens einem Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigten C3-C10-Mono- bzw. C4-C10-Dicarbonsäuren oder deren Anhydriden, wie Maleinsäure, Maleinsäureanhydrid, Acrylsäure, Methacrylsäure, Fumarsäure, Itaconsäure und Citraconsäure mit mindestens einem hydrophil oder hydrophob modifizierten Monomeren wie nachfolgend aufgezählt eingesetzt werden.It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or 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.
Geeignete hydrophobe Monomere sind beispielsweise Isobuten, Diisobuten, Buten, Penten, Hexen und Styrol, Olefine mit 10 oder mehr Kohlenstoffatomen oder deren Gemischen wie beispielsweise 1-Decen, 1-Dodecen, 1-Tetradecen, 1-Hexadecen, 1-Octadecen, 1-Eicosen, 1-Docosen, 1-Tetracosen und 1-Hexacosen, C22-α-Olefin, ein Gemisch aus C20-C24-α -Olefinen und Polyisobuten mit im Mittel 12 bis 100 C-Atomen pro Molekül.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 -α-olefin, a mixture of C 20 -C 24 -α-olefins and polyisobutene with an average of 12 to 100 carbon atoms per molecule.
Geeignete hydrophile Monomere sind Monomere mit Sulfonat- oder Phosphonatgruppen, sowie nichtionische Monomere mit Hydroxyfunktion oder Alkylenoxidguppen. Beispielsweise seien genannt: Allylalkohol, Isoprenol, Methoxypolyethylenglykol(meth)acrylat, Methoxypolypropylenglykol(meth)acrylat, Methoxypolybutylenglykol(meth)acrylat, Methoxypoly(propylenoxid-coethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypolypropylenglykol(meth)acrylat, Ethoxypolybutylenglykol(meth)acrylat und Ethoxypoly(propylenoxid-coethylenoxid)(meth)acrylat. Polyalkylenglykole können dabei 3 bis 50, insbesondere 5 bis 40 und vor allem 10 bis 30 Alkylenoxideinheiten pro Molekül enthalten.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.
Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acryl-amido-1-propansulfonsäure, 2-Acrylamido-2-propansulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Methacrylamido-2-methylpropansulfonsäure, 3-Meth-acrylamido-2-hydroxypropansulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Allyloxybenzolsulfonsäure, Methallyloxybenzolsulfonsäure, 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propen-1-sulfonsäure, Styrolsulfonsäure, Vinylsulfonsäure, 3-Sulfopropylacrylat, 2-Sulfoethylmethacrylat, 3-Sulfopropylmethacrylat, Sulfomethacrylamid, Sulfomethylmethacrylamid sowie Salze der genannten Säuren, wie deren Natrium-, Kalium oder Ammoniumsalze.Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.
Besonders bevorzugte Phosphonatgruppen-haltige Monomere sind die Vinylphosphonsäure und ihre Salze.Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
Darüber hinaus können auch amphotere Polymere als Builder eingesetzt werden.In addition, amphoteric polymers can also be used as builders.
Erfindungsgemäße Formulierungen können beispielsweise im Bereich von insgesamt 10 bis 50 Gew.-%, bevorzugt bis 20 Gew.-% Builder enthalten.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 einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen einen oder mehrere Cobuilder enthalten.In one embodiment of the present invention, formulations according to the invention may contain one or more co-builders.
Beispiele für Cobuilder sind Phosphonate, beispielsweise Hydroxyalkanphosphonate und Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH-Wert 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetra-methylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z.B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz des DTPMP, eingesetzt.Examples of co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably 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.
Erfindungsgemäße Formulierungen können einen oder mehrere Alkaliträger enthalten. Alkaliträger sorgen beispielsweise für den pH-Wert von mindestens 9, wenn ein alkalischer pH-Wert gewünscht wird. Geeignet sind beispielsweise Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallhydroxide und Alkalimetallmetasilikate. Bevorzugtes Alkalimetall ist jeweils Kalium, besonders bevorzugt ist Natrium.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.
Erfindungsgemäße Formulierungen können neben Bleichmittel (D) ein oder mehrere Chlor-haltige Bleichmittel enthalten.Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
Geeignete Chlor-haltige Bleichmittel sind beispielsweise 1,3-Dichloro-5,5-dimethylhydantoin, N-Chlorsulfamid, Chloramin T, Chloramin B, Natriumhypochlorit, Calciumhypochlorit, Magnesiumhypochlorit, Kaliumhypochlorit, Kaliumdichloroisocyanurat und Natriumdichloroisocyanurat.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.
Erfindungsgemäße Formulierungen können beispielsweise im Bereich von 3 bis 10 Gew.-% Chlor-haltiges Bleichmittel enthalten.For example, formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
Erfindungsgemäße Formulierungen können einen oder mehrere Bleichkatalysatoren enthalten. Bleichkatalysatoren kann man wählen aus bleichverstärkenden Übergangsmetallsalzen bzw. Übergangsmetallkomplexen wie beispielsweise Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdän-Salenkomplexe oder carbonylkomplexe. Auch Mangan-, Eisen-, Kobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden sowie Kobalt-, Eisen-, Kupfer- und Ruthenium-Aminkomplexe sind als Bleichkatalysatoren verwendbar.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.
Erfindungsgemäße Formulierungen können einen oder mehrere Bleichaktivatoren, beispielsweise N-Methylmorpholinium-Acetonitril-Salze ("MMA-Salze"), TrimethylammoniumacetonitrilSalze, N-Acylimide wie beispielsweise N-Nonanoylsuccinimid" 1,5-Diacetyl-2,2-dioxohexahydro-1,3,5-triazin ("DADHT") oder Nitrilquats (Trimethylammoniumacetonitrilsalze) enthalten.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).
Weitere Beispiele für geeignete Bleichaktivatoren sind Tetraacetylethylendiamin (TAED) und Tetraacetylhexylendiamin.Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
Erfindungsgemäße Formulierungen können einen oder mehrere Korrosionsinhibitoren enthalten. Darunter sind im vorliegenden Fall solche Verbindungen zu verstehen, die die Korrosion von Metall inhibieren. Beispiele für geeignete Korrosionsinhibitoren sind Triazole, insbesondere Benzotriazole, Bisbenzotriazole, Aminotriazole, Alkylaminotriazole, weiterhin Phenolderivate wie beispielsweise Hydrochinon, Brenzcatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin oder Pyrogallol.Formulations of the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin or pyrogallol.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,1 bis 1,5 Gew.-% Korrosionsinhibitor.In one embodiment of the present invention, formulations according to the invention contain a total of in the range of 0.1 to 1.5 wt .-% corrosion inhibitor.
Erfindungsgemäße Formulierungen können einen oder mehrere Gerüststoffe enthalten, beispielsweise Natriumsulfat.Formulations of the invention may contain one or more builders, for example, sodium sulfate.
Erfindungsgemäße Formulierungen können einen oder mehrere Entschäumer enthalten, gewählt beispielsweise aus Silikonölen und Paraffinölen.Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,05 bis 0,5 Gew.-% Entschäumer.In one embodiment of the present invention, formulations according to the invention contain in total in the range from 0.05 to 0.5% by weight defoamer.
Erfindungsgemäße Formulierungen können Phosphonsäure oder ein oder mehrere Phosphonsäurederivate enthalten, beispielsweise Hydroxyethan-1,1-diphosphonsäure.Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Geschirr und Küchenutensilien. Als Küchenutensilien sind im Rahmen der vorliegenden Erfindung beispielsweise Töpfe, Pfannen, Kasserollen zu nennen, weiterhin metallene Gegenstände wie beispielsweise Schaumlöffel, Bratenwender und Knoblauchpressen.Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils. As 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.
Bevorzugt ist die Verwendung von erfindungsgemäßen Formulierungen zur maschinellen Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, welches dekoriert oder nicht dekoriert sein kann. Dabei ist unter einer Oberfläche aus Glas im Rahmen der vorliegenden Erfindung zu verstehen, dass betreffender Gegenstand mindestens ein Stück aus Glas aufweist, das mit der Umgebungsluft in Berührung kommt und bei Gebrauch des Gegenstands verschmutzt werden kann. So kann es sich bei den betreffenden Gegenständen um solche handeln, die wie Trinkgläser oder Glasschüsseln im Wesentlichen gläsern sind. Es kann sich aber auch beispielsweise um Deckel handeln, die einzelne Komponenten aus einem anderen Material aufweisen, beispielsweise Topfdeckel mit Einfassung und Griff aus Metall.Preference is given to the use of formulations according to the invention for machine cleaning of articles which have at least one surface made of glass, which may be decorated or not decorated. In the context of the present invention, 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. Thus, 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.
Oberfläche aus Glas kann dekoriert, beispielsweise gefärbt oder bedruckt, oder nicht dekoriert sein.Glass surface may be decorated, for example colored or printed, or not decorated.
Unter dem Begriff "Glas" werden beliebige Gläser subsumiert, beispielsweise Bleiglas und insbesondere Kalknatronglas, Kristallglas und Borosilikatgläser.The term "glass" includes any glass, for example lead glass and in particular soda lime glass, crystal glass and borosilicate glasses.
Vorzugsweise handelt es sich bei maschineller Reinigung um ein Spülen mit einer Spülmaschine (englisch: automatic dishwashing").Machine cleaning is preferably dishwashing with a dishwasher (English: automatic dishwashing).
In einer Ausführungsform der vorliegenden Erfindung setzt man mindestens eine erfindungsgemäße Formulierung zur maschinellen Reinigung von Trinkgläsern, gläsernen Vasen und Glasgefäßen zum Kochen ein.In one embodiment of the present invention, at least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
In einer Ausführungsform der vorliegenden Erfindung setzt man zum Reinigen Wasser mit einer Härte im Bereich von 1 bis 30 °dH, bevorzugt 2 bis 25 °dH ein, wobei unter deutscher Härte insbesondere die Calcium-Härte zu verstehen ist.In one embodiment of the present invention, 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.
Auch zum Nachspülen kann man Wasser mit einer Härte im Bereich von 1 bis 30 °dH, bevorzugt 2 bis 25 °dH einsetzen.Also for rinsing water with a hardness in the range of 1 to 30 ° dH, preferably 2 to 25 ° dH can be used.
Setzt man erfindungsgemäße Formulierungen zur maschinellen Reinigung ein, so beobachtet man auch bei wiederholter maschineller Reinigung von Gegenständen, die mindestens eine Oberfläche aus Glas aufweisen, nur sehr geringe Neigung zur Glaskorrosion, und zwar selbst dann, wenn man Gegenstände, die mindestens eine Oberfläche aus Glas aufweisen, zusammen mit stark verschmutztem Besteck oder Geschirr reinigt. Außerdem ist es deutlich weniger schädlich, erfindungsgemäße Formulierung einzusetzen, um Glas zusammen mit Gegenständen aus Metall zu reinigen, beispielsweise zusammen mit Töpfen, Pfannen oder Knoblauchpressen.If 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.
Weiterhin kann man beobachten, dass erfindungsgemäße Formulierungen bei der Verwendung zum Spülen von Geschirr und Küchenutensilien und Glasoberflächen eine sehr gute Bleichwirkung aufweisen.Furthermore, it can be observed that formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen, kurz auch erfindungsgemäßes Herstellungsverfahren genannt. Zur Durchführung des erfindungsgemäßen Herstellungsverfahrens kann man beispielsweise so vorgehen, dass man
- (A) Aminocarboxylat, gewählt aus Methylglycindiacetat (MGDA), Iminodibernsteinsäure (IDS) und Glutaminsäurediacetat (GLDA) sowie deren Salzen, und
- (B) mindestens ein Alkylenimin-Polymer, das mit mindestens einer Carbonsäure oder mindestens einem Derivat einer Carbonsäure oder mindestens einem Derivat von Kohlensäure kovalent modifiziert ist, wobei bis maximal 75 mol-% der Stickstoff-Atome der primären und sekundären Aminogruppen des Alkylenimin-Polymers mit Carbonsäure bzw. Derivat von Carbonsäure bzw. Kohlensäure oder mit Blausäure und Formaldehyd umgesetzt sind,
und gegebenenfalls - (C) Natriumcitrat oder
- (D) mindestens eine Verbindung, gewählt aus Alkalimetallpercarbonat, Alkalimetallperborat und Alkalimetallpersulfat,
- (A) aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
- (B) at least one alkyleneimine polymer which is covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid, wherein 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 or with hydrogen cyanide and formaldehyde,
and optionally - (C) sodium citrate or
- (D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate,
Verbindung (A), modifiziertes Polyalkylenimin (B) und Bleichmittel (D) sind vorstehend definiert.Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
In einer Ausführungsform der vorliegenden Erfindung kann man, bevor man das Wasser zumindest teilweise entfernt, mit einem oder mehreren weiteren Inhaltsstoffen (E) für erfindungsgemäße Formulierung vermischen, beispielsweise mit einem oder mehreren Tenside, einem oder mehreren Enzymen, einem oder mehreren Buildern, einem oder mehrere Cobuildern, insbesondere Phosphor-freiem Builder, einem oder mehreren Alkaliträgern, einem oder mehreren Bleichmitteln, einem oder mehreren Bleichkatalysatoren, einem oder mehreren Bleichaktivatoren, einem oder mehreren Bleichmittelstabilisatoren, einem oder mehreren Entschäumern, einem oder mehreren Korrosionsinhibitoren, einem oder mehreren Gerüststoffen, mit Puffer oder Farbstoff.In one embodiment of the present invention, before at least partially removing the water, one may mix with one or more other ingredients (E) 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.
In einer Ausführungsform geht man so vor, dass man das Wasser ganz oder teilweise, beispielsweise bis zu einer Restfeuchte im Bereich von 0,1 bis 10 Gew.-% aus erfindungsgemäßer Formulierung entfernt, indem man es verdampft, insbesondere durch Sprühtrocknung, Sprühgranulierung oder Kompaktierung.In one embodiment, 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 ,
In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei einem Druck im Bereich von 0,3 bis 2 bar.In one embodiment of the present invention, the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.
In einer Ausführungsform der vorliegenden Erfindung entfernt man das Wasser, ganz oder teilweise, bei Temperaturen im Bereich von 60 bis 220°C.In one embodiment of the present invention, the water is removed, in whole or in part, at temperatures in the range of 60 to 220 ° C.
Durch das erfindungsgemäße Herstellungsverfahren kann man erfindungsgemäße Formulierungen leicht erhalten.By means of the preparation process according to the invention, it is easy to obtain formulations according to the invention.
Die erfindungsgemäßen Reinigungsformulierungen können in flüssiger oder fester Form, ein- oder mehrphasig, als Tabletten oder in Form anderer Dosiereinheiten, verpackt oder unverpackt bereitgestellt werden. Der Wassergehalt von flüssigen Formulierungen kann variieren von 35 bis 90% Wasser.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.
Die Erfindung wird durch Arbeitsbeispiele verdeutlicht.The invention is illustrated by working examples.
Allgemeines: Es wurde darauf geachtet, dass man nach dem ersten Reinigen der Prüfkörper in der Haushaltsgeschirrspülmaschine bis nach dem Wiegen und visuellen Abmustern der Gläser die Prüfkörper nur mit sauberen Baumwollhandschuhen angefasst wurden, damit das Gewicht bzw. der visuelle Eindruck der Prüfkörper nicht verfälscht wurde.General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.
Angaben in % sind Gew.-%, wenn nicht ausdrücklich anders angegeben.Data in% are wt .-%, unless expressly stated otherwise.
Die Ladungsdichte von modifizierten Polyethyleniminen (B) wurde stets wie folgt bestimmt (siehe auch: Horn, Prog. Colloid & Polym. Sci. 1978, 65, 251):The charge density of modified polyethylenimines (B) was always determined as follows (see also: Horn, Prog. Colloid & Polym Sci., 1978, 65 , 251):
Man löste 1 g des betreffenden (Co)polymers (B) in 100 ml vollentsalztem Wasser. Mit einer Pufferlösung und wässriger HCl stellte man einen pH-Wert von 4,0 ein, bestimmt potenziometrisch. Man setzte drei ml einer wässrigen Lösung von Toluidinblau (50 mg/l Wasser) zu und titrierte N/400-KPVS (Kaliumpolyvinylsulfat) Lösung (Fa. Wako) mit einer Konzentration von 0,0004 meq/ml bis zu einem Farbumschlag von blau nach rosa. Man berechnete die Ladungsdichte wie folgt:
- LA: Ladungsdichte des betreffenden modifizierten Polyethylenimins (B), meq/g (Milliäquivalent/g)
- KV: Verbrauch der N/400-KPVS-Lösung, ml
- LA: charge density of the respective modified polyethyleneimine (B), meq / g (milliequivalent / g)
- KV: consumption of N / 400 KPVS solution, ml
Zunächst wurden Basismischungen aus den Einsatzstoffen gemäß Tabelle 1 hergestellt. Die Einsatzstoffe wurden trocken vermischt.
Abkürzungen:
- MGDA: Methylglycindiessigsäure als Trinatriumsalz
- TAED: N,N,N',N'-Tetraacetylethylendiamin
- HEDP: Dinatriumsalz der Hydroxyethan-(1,1-diphosphonsäure)
- MGDA: methylglycine diacetic acid as trisodium salt
- TAED: N, N, N ', N'-tetraacetylethylenediamine
- HEDP: disodium salt of hydroxyethane (1,1-diphosphonic acid)
Es wurden modifizierte Polyethylenimine (B) gemäß Tabelle 2 verwendet:
Das Molgewicht Mw wurde an den zugrunde liegenden Polyethyleniminen bestimmt, also jeweils vor der Modifizierung. Die Funktionalisierung bezieht sich auf die Summe der primären und sekundären N-Atome im betreffenden Polyethylenimin.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.
In einem 100-ml-Becherglas legte man 20 ml destilliertes Wasser vor und gab modifiziertes Polyethylenimin (B) gemäß Tabellen 2 und 3 unter Rühren zu.
Dann rührte man 10 Minuten. Anschließend gab man MGDA-Trinatriumsalz (A.1), gelöst in 30 ml Wasser, gemäß Tabelle 3 zu. Man erhielt eine klar durchsichtige Lösung. Danach gab man Basismischung gemäß Tabelle 3 zu, rührte erneut um und verdampfte das Wasser.In a 100 ml beaker, 20 ml of distilled water was added and modified polyethyleneimine (B) according to Tables 2 and 3 added with stirring.
Then it was stirred for 10 minutes. Then, MGDA trisodium salt (A.1) dissolved in 30 ml of water was added as shown in Table 3. A clear solution was obtained. Thereafter, base mixture according to Table 3 was added, stirred again and evaporated the water.
Wenn man beim Test die entsprechenden Anteile Basismischung getrennt von wässriger Lösung von (A.1), (B), (C.1) oder (D.1) dosierte, erhielt man die gleichen Ergebnisse, wie wenn man die getrocknete Formulierung mit gleichen Mengen an Wirkstoffen testete. Es kommt also nicht auf die Reihenfolge der Dosierung an.If one dosed in the test, the appropriate proportions base mixture separately from aqueous solution of (A.1), (B), (C.1) or (D.1), gave the same results as when the dried formulation with the same Tested quantities of active ingredients. So it does not depend on the order of the dosage.
Wenn man bei der Kompaktierung zusätzlich 2,5 Gew.-% Polyvinylalkohol einsetzte, erhielt man Formulierungen mit verbesserter Pulvermorphologie (Korngröße, Schüttdichte) und einer verringerten Wasseraufnahme an der Luft.If additionally 2.5% by weight of polyvinyl alcohol were used in the compaction, formulations having improved powder morphology (particle size, bulk density) and a reduced water absorption in the air were obtained.
Allgemeines: Es wurde darauf geachtet, dass man nach dem ersten Reinigen der Prüfkörper in der Haushaltsgeschirrspülmaschine bis nach dem Wiegen und visuellen Abmustern der Gläser die Prüfkörper nur mit sauberen Baumwollhandschuhen angefasst wurden, damit das Gewicht bzw. der visuelle Eindruck der Prüfkörper nicht verfälscht wurde.General: Care was taken that after the first cleaning of the specimens in the household dishwasher until after weighing and visual patterning of the glasses, the specimens were only touched with clean cotton gloves, so that the weight or the visual impression of the specimens was not falsified.
Die Prüfung von erfindungsgemäßen Formulierungen und Vergleichsformulierungen erfolgte wie folgt.The testing of formulations according to the invention and comparative formulations was carried out as follows.
Zum Reinigen wurden die Gläser im oberen Geschirrkorb der Spülmaschine eingeordnet. Als Geschirrspülmittel setzte man jeweils 25 g erfindungsgemäße Formulierung oder 25 g Vergleichsformulierung gemäß Tabelle 2 ein, wobei Tabelle 2 die aktiven Komponenten (A.1), Basismischung , Silikat (C.1 oder C.2) und Verbindung (D) bzw. (E) und (B) von erfindungsgemäßer Formulierung jeweils einzeln spezifiziert. Man spülte bei einer Klarspültemperatur von 55°C. Die Wasserhärte lag jeweils im Bereich von null bis 2 °dH. Man spülte jeweils 100 Spülzyklen, d.h., man ließ das Programm 100 x ablaufen. Die Auswertung erfolgte gravimetrisch und visuell nach 100 Spülzyklen.For cleaning, 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. One rinsed 100 rinse cycles each, i.e., the program was run 100 times. The evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
Das Gewicht der Gläser wurde vor Beginn des ersten Spülzyklus und nach dem Trocknen nach dem letzten Spülzyklus bestimmt. Der Gewichtsverlust ist die Differenz der beiden Werte.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.
Neben der gravimetrischen Auswertung wurde eine visuelle Bewertung des Spülguts nach 100 Zyklen in einer abgedunkelten Kammer unter Licht hinter einer Lochblende unter Verwendung einer Notenskala von 1 (sehr schlecht) bis 5 (sehr gut) vorgenommen. Dabei wurden jeweils Noten für flächige Korrosion / Trübung bzw. Linienkorrosion bestimmt.In addition to the gravimetric evaluation, a visual assessment of the washware was made after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were determined.
Zunächst spülte man zum Zwecke der Vorbehandlung die Prüfkörper in einer Haushaltsgeschirrspülmaschine (Bosch SGS5602) mit 1 g Tensid (n-C18H37(OCH2CH2)10OH) und 20 g Zitronensäure, um eventuelle Verunreinigungen zu entfernen. Man trocknete die Prüfkörper, bestimmte ihr Gewicht und fixierte sie auf dem Gitterbodeneinsatz.First, for the purpose of pretreatment, 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.
Zur Beurteilung des gravimetrischen Abtrags wurden die trockenen Prüfkörper gewogen. Anschließend erfolgte die visuelle Beurteilung der Prüfkörper. Hierbei beurteilte man die Oberfläche der Prüfkörper hinsichtlich Linienkorrosion (Glasriefen) und Trübungskorrosion (flächenartige Trübung).To assess the gravimetric removal, 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).
Die Bewertungen erfolgten nach folgendem Schema.The assessments were made according to the following scheme.
- L5: keine Linien zu erkennenL5: no lines to recognize
- L4: in sehr wenigen Bereichen geringe Linienbildung, feine LinienkorrosionL4: in very few areas low line formation, fine line corrosion
- L3: in einigen Bereichen LinienkorrosionL3: line corrosion in some areas
- L2: in mehreren Bereichen LinienkorrosionL2: line corrosion in several areas
- L1: Stark ausgeprägte LinienkorrosionL1: Strong line corrosion
- T5: keine Trübung zu erkennenT5: no haze visible
- T4: in sehr wenigen Bereichen geringe TrübungT4: low turbidity in very few areas
- T3: in einigen Bereichen TrübungenT3: cloudiness in some areas
- T2: in mehreren Bereichen TrübungenT2: turbidity in several areas
- T1: Stark ausgeprägte Trübung über fast die ganze GlasoberflächeT1: markedly turbid over almost the entire glass surface
Bei der Bewertung wurden auch Zwischennoten (z.B. L3-4) zugelassen.Intermediate grades (e.g., L3-4) were also allowed in the evaluation.
Die Ergebnisse sind in Tabelle 3 zusammengefasst.The results are summarized in Table 3.
Es konnte in den erfindungsgemäßen Beispielen nur geringe oder gar keine Glaskorrosion festgestellt werden.It was found in the examples of the invention, little or no glass corrosion.
Wenn man statt Wasser Härtewasser mit 2° dH für die Tests einsetzte, so waren erfindungsgemäße Formulierungen den entsprechenden Vergleichsformulierungen ebenfalls stets überlegen, was die Inhibierung der Glaskorrosion betrifft.
Claims (14)
- A formulation comprising(A) in total in the range from 1 to 50% by weight of at least one aminocarboxylate, selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutaminic acid diacetate (GLDA), and salts thereof,(B) in total in the range from 0.001 to 5% by weight of at least one alkyleneimine polymer which is covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid, where up to at most 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer have been reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid or with hydrocyanic acid and formaldehyde,
- The formulation according to claim 1, which is free from phosphates and polyphosphates.
- The formulation according to claim 1 or 2, wherein covalently modified alkyleneimine polymer (B) is selected from alkyleneimine polymers(B1) which have been reacted with at least one ethylenically unsaturated C3-C10-carboxylic acid or(B2) which have been reacted with at least one C5-C12-carboxylic acid which has no ethylenic double bond,(B3) which have been reacted with at least one carbonic acid ester, and(B4) which have been reacted with hydrocyanic acid and formaldehyde.
- The formulation according to any one of claims 1 to 3, which has a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question.
- The formulation according to any one of claims 1 to 4, wherein alkyleneimine polymer (B) is selected from those in which in total 5 to 60 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer have been reacted with carboxylic acid or derivative of carboxylic acid.
- The formulation according to any one of claims 1 to 5, which is solid at room temperature.
- The formulation according to any one of claims 1 to 6, which comprises water in the range from 0.1 to 10% by weight.
- The formulation according to any one of claims 1 to 7, wherein covalently modified alkyleneimine polymer (B) has a catonic charge density of at least 5 meq/g.
- The use of formulations according to any one of claims 1 to 8 for washing crockery and kitchen utensils, where washing is carried out with water of hardness from 1 to 30° German hardness.
- The use of formulations according to any one of claims 1 to 8 for washing objects which have at least one surface made of glass, which can be decorated or undecorated.
- The use according to claim 9 or 10, wherein the washing is washing using a dishwasher.
- The use according to any one of claims 9 to 11, wherein at least one formulation according to any one of claims 1 to 8 is used for washing drinking glasses, glass vases and glass vessels for cooking.
- A process for the preparation of formulations according to any one of claims 1 to 8, wherein(A) Aminocarboxylate, selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDA) and glutaminic acid diacetate (GLDA), and salts thereof, and(B) at least one alkyleneimine polymer which is covalently modified with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid, where up to at most 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer have been reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid or with hydrocyanic acid and formaldehyde,and optionally further components are mixed in one or more steps with one another in the presence of water, and then the water is completely or partially removed.
- The process according to claim 13, wherein the water is removed by spray-drying or spray-granulation.
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PL13717782T PL2841548T3 (en) | 2012-04-25 | 2013-04-22 | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
EP13717782.0A EP2841548B1 (en) | 2012-04-25 | 2013-04-22 | Formulations, use of same as or for manufacture of dish-washing agents and their manufacture |
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GB201409632D0 (en) * | 2014-05-30 | 2014-07-16 | Reckitt Benckiser Brands Ltd | Improved detergent composition |
KR20170023947A (en) * | 2014-06-23 | 2017-03-06 | 바스프 에스이 | Formulations, use thereof as or for the production of dishwashing detergents, and production thereof |
ES2690336T3 (en) * | 2014-11-26 | 2018-11-20 | The Procter & Gamble Company | Cleaning bag |
MX2017006900A (en) * | 2014-11-26 | 2018-06-06 | Basf Se | Aqueous solution containing combination of complexing agents. |
RU2714202C2 (en) * | 2015-07-09 | 2020-02-13 | Басф Се | Dishware cleaning method |
MX2019000621A (en) | 2016-07-14 | 2019-08-01 | Basf Se | Fermentation medium comprising chelating agent. |
CN116583584A (en) * | 2020-12-07 | 2023-08-11 | 联合利华知识产权控股有限公司 | Detergent composition |
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JP3307952B2 (en) * | 1996-04-09 | 2002-07-29 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Anti-etching bottle cleaning solution |
US5837663A (en) | 1996-12-23 | 1998-11-17 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing tablets containing a peracid |
DE69826671T2 (en) * | 1997-07-23 | 2005-02-10 | Unilever N.V. | MACHINE DISHWASHER CONTAINING WATER-SOLUBLE CATIONIC OR AMPHOTERE POLYMERS |
DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
JP4015778B2 (en) * | 1999-06-17 | 2007-11-28 | ディバーシー・アイピー・インターナショナル・ビー・ヴイ | Liquid detergent composition for dishwashers |
EP1290126B1 (en) | 2000-06-14 | 2007-08-08 | The Procter & Gamble Company | Process for cleaning a surface |
DE10104469A1 (en) | 2001-02-01 | 2002-08-08 | Basf Ag | Copolymers to prevent glass corrosion |
JP4005855B2 (en) * | 2002-04-01 | 2007-11-14 | 株式会社日本触媒 | Detergent composition |
US7196044B2 (en) * | 2003-07-02 | 2007-03-27 | Ecolab, Inc. | Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor |
JP4942284B2 (en) * | 2003-09-26 | 2012-05-30 | 株式会社日本触媒 | Polyalkyleneimine derivatives and uses thereof |
DE102004005010A1 (en) * | 2004-01-30 | 2005-08-18 | Basf Ag | Polymer for the treatment of surfaces |
WO2006000020A1 (en) | 2004-06-29 | 2006-01-05 | European Nickel Plc | Improved leaching of base metals |
JP5025097B2 (en) * | 2005-06-02 | 2012-09-12 | ディバーシー・アイピー・インターナショナル・ビー・ヴイ | Liquid detergent composition for automatic washing machine |
ES2337914T3 (en) * | 2005-11-09 | 2010-04-30 | Ecolab Inc. | COMPOSITION WITH PROPERTIES OF SURFACE MODIFICATION. |
JP5213091B2 (en) * | 2006-08-22 | 2013-06-19 | ディバーシー株式会社 | Granular detergent composition for automatic dishwasher, method for producing the same, and method for using the same |
EP2245129B1 (en) * | 2008-01-24 | 2012-05-09 | Unilever N.V. | Machine dishwash detergent compositions |
EP2083067A1 (en) * | 2008-01-25 | 2009-07-29 | Basf Aktiengesellschaft | Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound |
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