EP3541911B1 - Preparations, their production and use - Google Patents

Preparations, their production and use Download PDF

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Publication number
EP3541911B1
EP3541911B1 EP17800781.1A EP17800781A EP3541911B1 EP 3541911 B1 EP3541911 B1 EP 3541911B1 EP 17800781 A EP17800781 A EP 17800781A EP 3541911 B1 EP3541911 B1 EP 3541911B1
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acid
weight
formulation
formulation according
alkyl
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German (de)
French (fr)
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EP3541911A1 (en
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Holger Tuerk
Heike Weber
Ditmar Kischkel
Juergen Franke
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • Cleaning agents for hard surfaces for example all-purpose kitchen cleaners and all-purpose bathroom cleaners, but also dishwashing detergents, hand washing-up liquids, glass cleaners, kitchen cleaners, bathroom and sanitary cleaners, toilet cleaners and disinfectant cleaners, often contain ingredients that make hard surfaces hydrophilic, which is why This means that water spreads better on such hard surfaces and water droplets form a film more quickly, which can then run off more easily.
  • EP 2 138 560 A1 disclose graft copolymers and their use in agents for cleaning hard surfaces, including as dishwashers.
  • the cleaning agents proposed still show a certain amount of deposit formation (so-called “filming” or “spotting”), especially on glass, ceramic and stainless steel, which is not an optimal result from the end user's point of view.
  • formulations which contain a graft copolymer and furthermore a builder selected from MGDA and GLDA and their salts.
  • the formulations disclosed show a good deposit inhibition - especially in phosphate-free dishwashing detergents and especially on glass. However, the formulations still have room for improvement for use as an all-purpose cleaner and as a rinse aid for dishes.
  • Another object was to provide a process by which formulations of this type can be produced.
  • formulations defined at the outset were found, also named formulations according to the invention in the context of the present invention.
  • Formulations according to the invention can be liquid, solid, paste-like or gel-like at room temperature, that is to say at 20 ° C.
  • Formulations according to the invention are preferably liquid at room temperature.
  • Formulations according to the invention which are solid at room temperature can be anhydrous or contain water, for example up to 20% by weight, preferably 0.1 to 10% by weight water, which can be determined for example by Karl Fischer titration or by determining the dry residue at 80 ° C under reduced pressure.
  • Formulations according to the invention which are solid at room temperature can, for example, be in the form of powder, granules or tablets.
  • formulations according to the invention are liquid at 20 ° C.
  • Formulations according to the invention which are liquid at 20 ° C. can contain 10 to 99.5% by weight of water, preferably 40 to 99% by weight, particularly preferably 80 to 99% by weight. In such embodiments, too, the water content can be determined by determining the dry residue at 80 ° C. under reduced pressure.
  • Formulations according to the invention which are liquid at room temperature can, for example, be in gel form, as a solution, suspension or emulsion.
  • Preferred nonionic surfactants (A) 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 polyglycosides and so-called amine oxides.
  • Compounds of the general formula (II) can be block copolymers or random copolymers, block copolymers are preferred.
  • Compounds of the general formula (III) can be block copolymers or random copolymers, block copolymers are preferred.
  • (AO) k is selected from (CH 2 CH 2 O) k1 , where k1 is selected from numbers in the range from 1 to 50.
  • (AO) k is selected from - (CH 2 CH 2 O) k2 - (CH 2 CH (CH 3 ) -O) k3 and - (CH 2 CH 2 O) k2 - (CH (CH 3 ) CH 2 -O) x3 , where k2 and k3 can be the same or different and are selected from numbers in the range from 1 to 30.
  • (AO) k is selected from - (CH 2 CH 2 O) k4 , where k4 is in the range from 10 to 50, AO is EO, and R 8 and R 9 independently of one another from C 8 -C 14 alkyl can be selected.
  • k or k1, k2, k3 and k4 are each mean values, the numerical mean being preferred. Therefore each of the variables k or k1, k2, k3 or k4 - if present - can mean a fraction. Of course, a particular molecule can only have a whole number of AO units.
  • suitable nonionic surfactants are selected from di- and multiblock copolymers, built up from ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are also suitable. An overview of other suitable nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187 .
  • It can also contain mixtures of several different nonionic surfactants.
  • compound (A) is selected from alcohol alkoxylates and alkyl polyglycosides. Alcohol alkoxylates are preferred.
  • Formulations according to the invention contain little or no MGDA and its salts. Formulations according to the invention contain little or no GLDA and its salts. Formulations according to the invention contain little or no citric acid and its salts. Specifically, formulations according to the invention contain (C) zero to a maximum of 0.5, preferably zero to 0.1% by weight of methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and alkali metal salts of MGDA and GLDA. In the context of the present invention, it is not important whether MGDA or GLDA or the corresponding salts are present in enantiomerically pure or racemic form or as an enantiomerically enriched mixture.
  • MGDA methylglycine diacetic acid
  • GLDA glutamic acid diacetic acid
  • formulations according to the invention contain from zero to 0.5% by weight of citric acid and the alkali metal salt of citric acid.
  • GLDA and MGDA and their alkali metal salts can be present as hydrates.
  • Citric acid itself and salts of citric acid are usually in the form of hydrates.
  • sodium citrate is usually present as a dihydrate and potassium citrate as a monohydrate under normal conditions.
  • quantitative data in connection with compound (A) always refer to the active ingredient, ie without taking hydrate into account.
  • quantitative data in connection with MGDA or GLDA or citric acid or its alkali metal salts always relate to the active ingredient, ie without taking hydrate into account.
  • Suitable nonionic monosaccharides as the graft base (a) can be selected, for example, from aldopentoses, pentuloses (ketopentoses), aldohexoses and hexuloses (ketohexoses).
  • Suitable aldopentoses are e.g. D-ribose, D-xylose and L-arabinose.
  • D-glucose, D-mannose and D-galactose may be mentioned as aldohexoses;
  • Examples of hexuloses (ketohexoses) are especially D-fructose and D-sorbose.
  • deoxy sugars such as L-fucose and L-rhamnose are also to be counted among non-ionic monosaccharides.
  • non-ionic disaccharides examples include cellobiose, lactose, maltose and sucrose.
  • nonionic carbohydrates with three to ten nonionic monosaccharide units per molecule are referred to as nonionic oligosaccharides.
  • non-ionic polysaccharides are non-ionic carbohydrates with more than ten non-ionic monosaccharide units per molecule.
  • Nonionic oligo- and polysaccharides can be linear, cyclic or branched, for example.
  • non-ionic polysaccharides examples include biopolymers such as starch and glycogen as well as cellulose and dextran. Also to be mentioned are inulin as a polycondensate of D-fructose (fructans) and chitin. Further examples of non-ionic polysaccharides are non-ionic starch degradation products, for example products which can be obtained by enzymatic or so-called chemical degradation of starch. An example of the so-called chemical breakdown of starch is acid-catalyzed hydrolysis.
  • maltodextrins Preferred examples of non-ionic starch degradation products are maltodextrins.
  • maltodextrin is understood to mean mixtures of monomers, dimers, oligomers and polymers of glucose. The percentage composition differs depending on the degree of hydrolysis. This is described by the dextrose equivalent, which is between 3 and 40 for maltodextrin.
  • the graft base (a) is preferably chosen from nonionic polysaccharides, in particular from starch, which is preferably not chemically modified, for example whose hydroxyl groups are preferably neither esterified nor etherified.
  • starch is selected from those nonionic polysaccharides which have in the range from 20 to 30% by weight amylose and in the range from 70 to 80% amylopectin. Examples are corn starch, rice starch, potato starch and wheat starch.
  • Side chains are grafted onto the graft base (a).
  • An average of one to ten side chains can preferably be grafted on per molecule of graft copolymer (B).
  • a side chain is preferably linked to the anomeric carbon atom of a monosaccharide or to an anomeric carbon atom of the chain end of an oligo- or polysaccharide. The number of side chains is limited by the number of carbon atoms with hydroxyl groups of the graft base (a) in question.
  • monocarboxylic acids (b) are ethylenically unsaturated C 3 -C 10 monocarboxylic acids and their alkali metal or ammonium salts, in particular the potassium and sodium salts.
  • Preferred monocarboxylic acids (b) are acrylic acid and methacrylic acid and sodium (meth) acrylate.
  • Mixtures of ethylenically unsaturated C 3 -C 10 monocarboxylic acids and in particular mixtures of acrylic and methacrylic acid are also preferred components (b).
  • dicarboxylic acids (b) are ethylenically unsaturated C 4 -C 10 dicarboxylic acids and their mono- and especially dialkali metal or ammonium salts, in particular the dipotassium and disodium salts, and anhydrides of ethylenically unsaturated C 4 -C 10 dicarboxylic acids.
  • Preferred dicarboxylic acids (b) are maleic acid, fumaric acid, itaconic acid and maleic anhydride and itaconic anhydride.
  • graft copolymer (B) contains at least one side chain in addition to monomer (c) at least one monocarboxylic acid (b) and at least one dicarboxylic acid (b).
  • graft copolymer (B) contains, in addition to monomer (c), exclusively monocarboxylic acid (b) in the side chains, but no dicarboxylic acid (b) in copolymerized form.
  • monomer (c) is selected from
  • Graft copolymer (B) can contain at least one further comonomer (d) in copolymerized form in one or more side chains, for example hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, or esters of alkoxylated fatty alcohols, or comonomers containing sulfonic acid groups, for example 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts.
  • hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate
  • esters of alkoxylated fatty alcohols or comonomers containing sulfonic acid groups, for example 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • graft copolymer (B) preferably contains no further comonomers (d) in one or more side chains.
  • the proportion of graft base (a) in graft copolymer (B) is in the range from 40 to 95% by weight, preferably from 50 to 90% by weight, based in each case on the total graft copolymer (B).
  • the proportion of monocarboxylic acid (b) or dicarboxylic acid (b) is in the range from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 5 to 25% by weight , in each case based on the total graft copolymer (B).
  • Monomer or monomers (c) is or are polymerized in amounts of 5 to 50% by weight, preferably 5 to 40% by weight and particularly preferably 5 to 30% by weight, each based on the total graft copolymer ( B).
  • graft copolymer (B) contains more monocarboxylic acid (b) than monomer (c) in copolymerized form, based on the molar proportions, for example in the range from 1.1: 1 to 5: 1, preferably 2: 1 to 4 :1.
  • the average molecular weight (M w ) of graft copolymer (B) is in the range from 1,500 to 200,000 g / mol, preferably from 2,000 to 150,000 and in particular in the range from 3,000 to 100,000 g / mol.
  • the average molecular weight M w is preferably measured by gel permeation chromatography in an aqueous KCl / formic acid solution.
  • Graft copolymer (B) can preferably be obtained as an aqueous solution from which it can be isolated, e.g. B. by spray drying, spray granulation or freeze drying. Alternatively, a solution of graft copolymer (B) or dried graft copolymer (B) can be used for the preparation of the formulations according to the invention.
  • biocides for example 1,2-benzisothiazolin-3-one ("BIT"), octylisothiazolinone ("OIT”), dichloroctylisothiazolinone ("DCOIT”), 2-methyl-2 H -isothiazolin-3-one ( "MIT”) and 5-chloro-2-methyl-2 H -isothiazolin-3-one (“CIT”), phenoxyethanol, alkyl parabens such as methyl paraben, ethyl paraben, propyl paraben, benzoic acid and its salts such as sodium benzoate, benzyl alcohol, alkali metal sorbates such as Sodium sorbate and optionally substituted hydantoins such as, for example, 1,3-bis (hydroxymethyl) -5,5-dimethylhydantoin (DMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDMDM
  • the formulation according to the invention is free from phosphates and polyphosphates, hydrogen phosphates also being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate.
  • “free of” should be understood in the context of the present invention that the total content of phosphate and polyphosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry.
  • the formulation according to the invention is free from those heavy metal compounds which do not act as bleach catalysts, in particular from compounds of iron.
  • “free of” is to be understood as meaning that the total content of heavy metal compounds that do not act as bleach catalysts is in the range from 0 to 100 ppm, preferably 1 to 30 ppm, determined according to the Leach method.
  • heavy metals are all metals with a specific density of at least 6 g / cm 3 , with the exception of zinc and bismuth.
  • heavy metals are precious metals such as iron, copper, lead, tin, nickel, cadmium and chromium.
  • formulation according to the invention contains
  • compound (A) in total in the range from 20 to 99% by weight of compound (A), preferably 40 to 98% by weight, particularly preferably 50 to 95% by weight, and in total in the range from 1 to 40% by weight of graft copolymer (B), preferably 3 to 30% by weight, particularly preferably 5 to 20% by weight, based in each case on the solids content of the formulation in question.
  • the weight ratio of compound (A) to graft copolymer (B) is preferably in the range from 1: 2 to 20: 1.
  • liquid formulations according to the invention contain
  • compound (A) in total in the range from 20 to 99.9% by weight of compound (A), preferably 40 to 98% by weight, particularly preferably 50 to 95% by weight, and in total in the range from 0.01 to 40% by weight of graft copolymer (B), preferably 3 to 30% by weight, particularly preferably 5 to 20% by weight, based in each case on the aqueous formulation according to the invention in question.
  • Formulations according to the invention can be free from bleaching agents, for example free from inorganic peroxide compounds or chlorine bleaching agents such as sodium hypochlorite.
  • Free from inorganic peroxide compounds or chlorine bleaching agents should be understood to mean that such formulations according to the invention contain a total of 0.01% by weight or less of inorganic peroxide compounds and chlorine bleaching agents, based in each case on the solids content of the formulation according to the invention in question.
  • formulation according to the invention contains (D) at least one inorganic peroxide compound, also referred to for short in the context of the present invention as peroxide (D).
  • Peroxide (D) is selected from hydrogen peroxide, sodium peroxodisulfate, sodium perborate and sodium percarbonate, sodium percarbonate is preferred.
  • Sodium percarbonate is preferred in solid formulations according to the invention and hydrogen peroxide is preferred in liquid formulations according to the invention.
  • Solid peroxide (D) can be anhydrous or preferably contain water.
  • hydrous sodium perborate Na 2 [B (OH) 2 (O 2 )] 2 ), sometimes also written as NaBO 2 ⁇ O 2 ⁇ 3H 2 O.
  • An example of sodium percarbonate containing water is 2 Na 2 CO 3 ⁇ 3 H 2 O 2 .
  • Solid peroxide (D) is particularly preferably chosen from hydrous percarbonates.
  • Percarbonates and in particular sodium percarbonate are preferably used in coated form.
  • the coating can be of an inorganic or organic nature.
  • coating agents are glycerol, sodium sulfate, silica gel, sodium silicate, sodium carbonate and combinations of at least two of the above coating agents, for example sodium carbonate and sodium sulfate.
  • Solid formulations according to the invention preferably contain in the range from 1 to 30% by weight peroxide (D), preferably 2 to 15% by weight, particularly preferably 3 to 12% by weight, based on the solids content of the solid formulation in question.
  • D peroxide
  • Liquid formulations according to the invention preferably contain in the range from 1 to 30% by weight of peroxide (D), preferably 2 to 15% by weight, particularly preferably 3 to 12% by weight, based in each case on the solids content of the formulation in question.
  • peroxide (D) is preferably hydrogen peroxide.
  • Formulations according to the invention which contain at least one peroxide (D) are preferably liquid at room temperature.
  • formulation according to the invention contains (D) at least one chlorine-containing bleach, which in the context of the present invention is also referred to for short as chlorine bleach (D).
  • Chlorine bleach (D) is preferably sodium hypochlorite.
  • Chlorine bleach (D) -containing formulations according to the invention are preferably liquid at room temperature.
  • the formulation according to the invention preferably contains in the range from 0.1 to 30% by weight of chlorine bleach (D), preferably 0.5 to 15% by weight, particularly preferably 1 to 12% by weight, based on the solids content of the liquid formulation in question.
  • D chlorine bleach
  • Formulations according to the invention can contain one or more further ingredients (E).
  • Ingredients (E) are different from compound (A), graft copolymer (B) and peroxide (D) or chlorine bleach (D).
  • Formulations according to the invention can have one or more further ingredients (E), for example one or more anionic or zwitterionic surfactants, one or more enzymes, one or more enzyme stabilizers, one or more alkali carriers, one or more acids, 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, colorants, one or more fragrances, one or more thickeners, one or more organic solvents, one or more tabletting aids, one or more Disintegration agents, also called tablet disintegrants, or one or more solubilizers.
  • anionic or zwitterionic surfactants for example one or more anionic or zwitterionic surfactants, one or more enzymes, one or more enzyme stabilizers, one or more alkali carriers, one or more acids, one or more bleach catalysts, one or more Bleach activators, one or more bleach stabilizers, one or more defoamers, one or
  • anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates with one to 6 ethylene oxide units per molecule, for example those of the following formula: R 12 -O (CH 2 CH 2 O) u -SO 3 M
  • R 12 is C 8 -C 20 -alkyl, branched or preferably unbranched
  • the variable u is in the range from 1 to 6
  • amphoteric surfactants are those substances which have a positive and a negative charge under application conditions.
  • amphoteric surfactants also known as zwitterionic surfactants are so-called amine oxide surfactants and betaines or betaine surfactants.
  • amine oxide surfactants and betaines or betaine surfactants.
  • betaines have one quaternized nitrogen atom and one carboxylic acid group per molecule.
  • a particularly preferred example is cocoamidopropyl betaine.
  • amine oxide surfactants are compounds of the general formula (VII) R 13 R 14 R 15 N ⁇ O (VII) where R 13 , R 14 and R 15 are selected independently of one another from aliphatic or cycloaliphatic or C 2 -C 4 -alkylene or C 10 -C 20 -alkylamido groups.
  • R 13 is particularly preferably selected from C 8 -C 20 -alkyl or C 2 -C 4 -alkylenes, C 10 -C 20 -alkylamido and R 14 and R 15 are each methyl.
  • Particularly preferred examples are lauryl dimethalamine oxide and cocoamidopropylamine oxide.
  • the formulation according to the invention can contain in the range from 3 to 50% by weight of anionic or zwitterionic surfactant.
  • Formulations according to the invention can contain one or more enzymes.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
  • Formulations according to the invention can contain, for example, up to 5% by weight of enzyme, 0.1 to 3% by weight are preferred, in each case based on the total solids content of the formulation according to the invention.
  • Formulations according to the invention can contain one or more enzyme stabilizers.
  • Enzyme stabilizers serve to protect enzymes - especially during storage - against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage.
  • enzyme stabilizers are reversible protease inhibitors, for example benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, including, in particular, derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, especially 4-formylphenylboronic acid, or the salts or esters of the aforementioned compounds.
  • Peptide aldehydes that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose.
  • the peptide reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids up to C 12 -carboxylic acids, such as succinic acid. End-capped fatty acid amide alkoxylates are also suitable enzyme stabilizers.
  • enzyme stabilizers are sodium sulfite, reducing sugars, and potassium sulfate.
  • Another example of a suitable enzyme stabilizer is sorbitol.
  • Formulations according to the invention can contain one or more builders (E), in particular phosphate-free builders (E).
  • compound (A) does not count as builder (E).
  • suitable builders (E) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , furthermore ethylenediamine disuccinic acid and polymeric builders (E), for example polycarboxylates and polyaspartic acid.
  • Formulations according to the invention very particularly preferably contain one or more polymeric builders (E).
  • Polymeric builders (E) are understood to mean organic polymers, in particular polycarboxylates and polyaspartic acid. Polymer builders (E) have no or only a negligible effect as a surfactant.
  • polymeric builders (E) are selected from polycarboxylates, 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 acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
  • polymeric builders (E) are selected from one or more copolymers, prepared from at least one monomer from the group consisting of monoethylenically unsaturated C 3 -C 10 mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, Acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid and at least one hydrophilic or hydrophobic comonomer, 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 such as, 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.
  • Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups and nonionic monomers with a hydroxyl 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-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate,
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-meth-acrylamido-2- hydroxypropanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen-1-sulphonic acid, styrene-propene-1-sulphonic acid, 3-sulphate-2-sulpho-methacrylate, 3-sulphacrylate-2-sulpho-methacrylate, Sulfomethacrylamide, sulfomethyl methacrylamide and salts of the aforementioned acids, e.g. B.
  • Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.
  • amphoteric polymers other than graft polymer (B) can be used as polymeric builders (E).
  • amphoteric polymers are copolymers of at least one ethylenically unsaturated carboxylic acid selected from acrylic acid and methacrylic acid, at least one amide selected from NC 1 -C 10 -alkyl (meth) acrylamide, acrylamide and methacrylamide, and at least one comonomer selected from DADMAC, MAP-TAC and APTAC.
  • Formulations according to the invention can contain, for example, in the range from a total of 1 to 75% by weight, preferably up to 50% by weight, of builder (E), based on the solids content of the formulation according to the invention in question.
  • Formulations according to the invention can contain, for example, in the range from a total of 1 to 15% by weight, preferably up to 10% by weight, of polymeric builders (E), based on the solids content of the formulation according to the invention in question.
  • polymeric builders E
  • the formulation according to the invention comprises, in addition to graft polymer (B), a polymeric builder (E).
  • the weight ratio of polymeric builder (E) to graft copolymer (B) is then preferably from 30: 1 to 1: 3, particularly preferably from 20: 1 to 1: 1.
  • formulations according to the invention can contain one or more co-builders.
  • cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
  • hydroxyalkanephosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9).
  • Ethylenediamine tetra-methylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferably used as aminoalkanephosphonates. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP.
  • Formulations according to the invention can contain one or more alkali carriers.
  • Alkali carriers for example, ensure a pH value of at least 9 if an alkaline pH value is desired.
  • alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates are suitable.
  • the preferred alkali metal in each case is potassium, and sodium is particularly preferred.
  • organic amines, alkanolamines such as e.g. Triethanolamine, or ammonia can be used.
  • Formulations according to the invention can 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-salen complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.
  • Formulations according to the invention can contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3 , 5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3
  • DADHT 5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • Formulations according to the invention can contain one or more corrosion inhibitors.
  • these are to be understood as meaning those compounds which inhibit the corrosion of metal.
  • suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol, furthermore polyethyleneimine and salts of bismuth or zinc.
  • formulations according to the invention contain a total of in the range from 0.1 to 1.5% by weight of corrosion inhibitor, based on the solids content of the formulation according to the invention in question.
  • Formulations according to the invention can contain one or more builders, for example sodium sulfate.
  • Formulations according to the invention can contain one or more defoamers, selected for example from silicone oils and paraffin oils.
  • formulations according to the invention contain a total of in the range from 0.05 to 0.5% by weight of defoamers, based on the solids content of the formulation according to the invention in question.
  • formulations according to the invention can contain one or more acids.
  • Organic acids and inorganic acids are suitable.
  • organic acids for example methanesulfonic acid, formic acid, acetic acid, glycolic acid, lactic acid, succinic acid and / or adipic acid can be selected.
  • the inorganic acid used is preferably hydrochloric acid or phosphoric acid or sulfamic acid. Mixtures of acids can also be used, including mixtures of organic and inorganic acids.
  • the use of acids in formulations according to the invention comes into consideration in particular if the corresponding cleaner should also have improved lime, rust or urine scale removal in addition to the advantages according to the invention, for example in shower cleaners, bathroom cleaners or toilet cleaners.
  • solid formulations according to the invention contain one or more disintegrants, also called tablet disintegrants.
  • disintegrants also called tablet disintegrants.
  • examples are starch, polysaccharides, for example dextrans, furthermore crosslinked polyvinylpyrrolidone and polyethylene glycol sorbitan fatty acid esters.
  • such formulations according to the invention which are liquid at room temperature contain one or more thickeners.
  • gel-like formulations according to the invention are preferably added one or more thickeners, it being particularly advantageous if the formulation according to the invention in question has thickeners in the range from 0.5 to 30% by weight, preferably from 1 to 20% by weight and particularly preferably from 2 to 15% by weight, based on the solids content of the formulation according to the invention in question.
  • thickener you can choose polymers derived from nature or modified natural substances or synthetic thickeners.
  • polymers derived from nature which are suitable as thickeners in the context of the present invention include: agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob gum, starch, dextrins , Xanthan, gelatin and casein.
  • thickeners from the group of modified natural substances can be chosen, for example, from the group of modified starches and celluloses.
  • Carboxymethyl cellulose and other cellulose ethers, hydroxyethyl cellulose and hydroxypropyl cellulose and gum ethers may be mentioned as examples.
  • Synthetic thickeners are selected from partially cross-linked poly (meth) acrylic acids, hydrophobically modified polyurethanes (HEUR thickeners) and poly (meth) acrylic acid copolymers esterified with fatty alcohol ethoxylates (HASE thickeners).
  • a particularly preferred thickening agent used is xanthan.
  • formulations according to the invention can contain one or more synthetic or natural waxes; carnauba wax is particularly preferred. Wax is specially added to finish sensitive surfaces, for example in floor cleaners.
  • formulations according to the invention can contain one or more organic solvents.
  • organic solvents can be chosen from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides.
  • Organic solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
  • Organic solvents which are suitable for formulations according to the invention are preferably chosen from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers which are miscible with water in the specified concentration range.
  • Organic solvents are preferably chosen from ethanol, n-propanol, isopropanol, butanols, glycol, 1,2-propanediol, or butanediol, glycerol, diglycol, propyl or n-butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or but
  • formulations according to the invention have a pH value in the range from 1 to 6, preferably 1 to 4.
  • the pH value is 1% by weight. % aqueous solution or the liquid phase of a 1 wt .-% aqueous suspension determined.
  • formulations according to the invention have a pH value in the range from 6 to 14, preferably 7 to 10.
  • the pH value of 1 wt .-% aqueous solution or the liquid phase of a 1 wt .-% aqueous suspension determined.
  • Formulations according to the invention are very well suited as or for the production of rinse aids for dishwashing, in particular for automatic dishwashing (ADW for short).
  • Formulations according to the invention themselves and dishwashing detergents produced from formulations according to the invention - in particular phosphate-free dishwashing detergents produced from formulations according to the invention - have very good deposit inhibition in dishwashing, in particular on items made of glass.
  • formulations according to the invention are also effective against stubborn stains.
  • Examples of metal items to be washed are cutlery, pots, pans and garlic presses, in particular cutlery items such as knives, cake servers and cutlery.
  • Examples of items to be washed made of glass include: glasses, glass bowls, glass dishes such as glass plates, but also objects that have at least one surface made of glass that may or may not be decorated, for example glass vases, transparent pot lids and glass vessels Cook.
  • Plates, cups, mugs and bowls made of melamine, polystyrene and polyethylene may be mentioned as examples of items to be washed made of plastic.
  • Examples of items to be washed made of porcelain are plates, cups, mugs and bowls made of porcelain, white or colored, each with or without decoration.
  • Formulations according to the invention are suitable not only as or for the production of dishwashing detergents, but as or for the production of cleaning compositions for hard surfaces, for example floor cleaners, all-purpose kitchen cleaners or all-purpose bathroom cleaners.
  • an acidic pH is preferred, for example in the range from 1 to 6.5.
  • a neutral or alkaline pH is preferred, for example in the range from 7 to 10.
  • di- or polycarboxylic acids such as acetic acid or tartaric acid can be used.
  • Floor cleaners and all-purpose cleaners are intended for use in cleaning sensitive surfaces and usually have a pH value in the range of approx. 5 to 8. In many variants, floor cleaners and all-purpose cleaners also contain care products such as waxes for the care of the surfaces. The same applies to washing-up liquids and paint cleaners, e.g. B. for automobiles. Kitchen cleaners preferably have a pH value of 8 to 14 and, thanks to the strongly alkaline pH value, achieve optimum fat removal or fat removal.
  • Bath, shower and toilet cleaners preferably have an acidic pH value, for example from 1 to 5, and achieve optimal limescale or urine scale removal due to the strongly acidic pH value. If you want to add bleach to the bathroom, shower or toilet cleaners, combinations of chlorine bleach based on hypochlorite with base are preferred. Another preferred combination is peroxide bleaching agents such as hydrogen peroxide with acids. Such combinations have a better storage stability.
  • hard surfaces are surfaces of materials which are not water-soluble and preferably also not swellable under cleaning conditions. Preferably they have a Mohs hardness of 3 or more. Examples include: tiles, glass, fiberglass, tiles, ceramics, porcelain, enamel, concrete, stone materials, leather, metals and alloys such as iron, aluminum and steel, hardwood, painted surfaces and coatings, polymers and plastics such as polyethylene, polypropylene , PMMA, polycarbonates, polyesters such as PET, polystyrene and rigid PVC, fiber-reinforced Plastics such as laminate, silicon surfaces, for example wafers, and composite materials. Hard surfaces can appear smooth to the human eye or they can have a structure, for example elevations or depressions, for example furrows, and they can be convex or concave.
  • Tiles and tiles can, for example, belong to bathrooms, kitchens, hospitals or machines.
  • the present invention also provides a process for the production of formulations according to the invention, also called production process according to the invention in the context of the present invention.
  • the production process according to the invention is characterized in that at least one compound (A), at least one graft copolymer (B) and optionally one or more further ingredients (E) and optionally peroxide (D) or chlorine bleach (D) with one another in one or more steps mixed, if appropriate in the presence of water, and then if appropriate, water is completely or partially removed.
  • compound (A), one or more further ingredients (E) and optionally peroxide (D) are mixed in dry form and then an aqueous solution of graft copolymer (B) is added, either outside or inside a dishwasher .
  • compound (A), graft copolymer (B) and one or more further ingredients (E) and optionally peroxide (D) or chlorine bleach (D) are mixed in dry form and the mixture thus obtained is compressed to form molded articles , especially about tablets.
  • the water before the water is at least partially removed, it can be mixed with one or more further ingredients (E) for the formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more enzyme stabilizers, one or more several builders (E), preferably one or more phosphate-free builders (E), in particular one or more polymer builders (E), one or more cobuilders, one or more alkali carriers, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, with a buffer or dye.
  • one or more surfactants for example with one or more surfactants, one or more enzymes, one or more enzyme stabilizers, one or more several builders (E), preferably one or more phosphate-free builders (E), in particular one or more polymer builders (E), one or more cobuilders, one or more alkali carriers, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizer
  • the procedure is such that the water is completely or partially removed, for example down to a residual moisture content in the range from zero to 15% by weight, preferably 0.1 to 10% by weight, from the formulation according to the invention by removing it evaporated, in particular by spray drying, spray granulation or compaction.
  • all or part of the water is removed at a pressure in the range from 0.3 to 2 bar.
  • all or part of the water is removed at temperatures in the range from 60 to 220.degree.
  • liquid formulations according to the invention can be obtained in this way. At room temperature, liquid formulations according to the invention can be in gel form, as an emulsion or as a solution, for example.
  • Formulations according to the invention can easily be obtained by the production process according to the invention.
  • formulations according to the invention can be provided in liquid or solid form, in one or more phases, as tablets or in the form of other dosage units, for example as so-called pouches, packaged or unpacked.
  • the biocide used was a 9% by weight solution of 1,2-benzisothiazolin-3-one in a water / propylene glycol mixture, commercially available as Proxel TM XL2 Antimicrobial. Quantities in g are tell qu'elle.
  • Formulations KSF.3 according to the invention and comparative formulations V-KSF.1 and V-KSF.2 were produced.
  • the components of the comparative formulations V-KSF.1 and V-KSF.2 and the formulation KSF.3 according to the invention are shown in Table 1.
  • Isopropanol, anionic surfactant and non-ionic surfactant and finally the copolymer (B.1) were then added with stirring.
  • Table 1 Composition of comparative formulations V-KSF.1 and V-KSF.2 and of formulation KSF.3 according to the invention V-KSF.1 V-KSF.2 KSF.3 Feedstock Conc.
  • Nio surfactant 1 95% 5% 2.6 5% 2.6 5% 2.6
  • Anion surfactant 1 40% 10% 12.5 10% 12.5 10% 12.5 Isopropanol 100% 5% 2.5 5% 2.5 5% 2.5 5% 2.5 VP.1 22% - - 1% 2.3 - - (B.1) 22.4% - - - - 1% 2.3 VE water 80% 32.4 79% 30.1 79% 30.1 Batch size [g] 50 50 50 Appearance clear, colorless clear, slightly yellowish clear, colorless Concentrations are always given in% by weight Nio surfactant 1: nC 16 H 33 -O- (C 2 H 4 O) 25 -OH
  • Anion surfactant 1 sodium cumene sulfonate
  • the comparative polymer VP.1 was made according to Example 4 EP 2 138 560 B1 manufactured.
  • the dishes were removed from the machine after drying.
  • Table 2 Composition of the formulation for scale inhibition tests Component [g] Racemic MGDA-Na 3 , 78% by weight, the remainder is water 10 Citric acid as a trisodium salt monohydrate 35 Polyacrylic acid M w 4,000 g / mol as the sodium salt, completely neutralized 5 Sodium percarbonate, 2 Na 2 CO 3 • 3 H 2 O 2 10.2 Non-ionic surfactant 1 4th Non-ionic surfactant 2 1 Protease 2.5 Amylase 1 Na 2 Si 2 O 5 , commercially available as Britesil® H 265 LC 2 TAED 4th Na 2 CO 3 24.5 1-Hydroxyethane-1,1-diphosphonate disodium salt 0.8
  • Liquid cleaning formulation RF.1 according to the invention and liquid comparison formulations V-RF.2 and V-RF.3 were produced by producing or using the components according to Table 4 in each case as aqueous solutions and then mixing them.
  • Nonionic surfactant 4 0.25 0.25 0.25 (B.1) 0.1 0 0 VP.1 0 0.1 0 water
  • Nonionic surfactant 4 2-n-propylheptanol, ethoxylated with 6 equivalents of ethylene oxide
  • the IPP form as published in S ⁇ FW, NO10 / 1986, page 371, was used to determine the primary cleaning performance.
  • An artificial IPP pollution (83/21) of the following composition was used for the test: 40% Nytex 801 (mineral oil), 36% petrol 80/110, 70% Myritol 318 (triglyceride) and 7% special black 4.
  • the mineral oil, myritol and petrol were mixed and the special black was slowly stirred in.
  • the mixture obtained in this way was homogenized with an Ultraturrax device for 30 minutes at speed 4-5 and then aged for 21 days in a closed Erlenmeyer flask on a stir plate. It was then homogenized again for 30 minutes.

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Description

Die vorliegende Anmeldung betrifft Formulierungen, enthaltend

  1. (A) mindestens ein nicht-ionisches Tensid,
  2. (B) mindestens ein Pfropfcopolymer, aufgebaut aus
    1. (a) mindestens einer Pfropfgrundlage, gewählt aus nicht-ionischen Monosacchariden, Disacchariden, Oligosacchariden und Polysacchariden, und Seitenketten, erhältlich durch Aufpfropfen von
    2. (b) mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure und
    3. (c) mindestens einer Verbindung der allgemeinen Formel (I),
      Figure imgb0001
       wobei die Variablen wie folgt definiert sind:
      • R1 ist gewählt aus Methyl und Wasserstoff,
      • A1 ist gewählt aus C2-C4-Alkylen,
      • R2 sind gleich oder verschieden und gewählt aus C1-C4-Alkyl,
      • X- ist gewählt aus Halogenid, Mono-C1-C4-Alkylsulfat und Sulfat,
  3. (C) insgesamt von null bis 0,5 Gew.-% Methylglycindiessigsäure (MGDA) und Glutaminsäurediessigsäure (GLDA) und Alkalimetallsalze von MGDA und GLDA, und insgesamt null bis 0,5 Gew.-% Citronensäure und Alkalimetallsalz von Citronensäure.
The present application relates to formulations containing
  1. (A) at least one non-ionic surfactant,
  2. (B) at least one graft copolymer built up from
    1. (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on
    2. (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and
    3. (c) at least one compound of the general formula (I),
      Figure imgb0001
       where the variables are defined as follows:
      • R 1 is selected from methyl and hydrogen,
      • A 1 is selected from C 2 -C 4 alkylene,
      • R 2 are identical or different and are selected from C 1 -C 4 -alkyl,
      • X- is selected from halide, mono-C 1 -C 4 -alkyl sulfate and sulfate,
  3. (C) a total of from zero to 0.5 weight percent methylglycinediacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and alkali metal salts of MGDA and GLDA, and a total of zero to 0.5 weight percent citric acid and alkali metal salt of citric acid.

Reinigungsmittel für harte Oberflächen, beispielsweise Allzweck-Küchenreiniger und Allzweck-Badreiniger, aber auch Geschirrspülmittel, Handspülmittel, Glasreiniger, Küchenreiniger, Bad- und Sanitärreiniger, WC-Reiniger und Desinfektionsreiniger, enthalten häufig Inhaltsstoffe, die zu einer Hydrophilierung von harten Oberflächen führen, was dazu führt, dass Wasser auf derartigen harten Oberflächen besser spreitet und Wassertropfen schneller einen Film bilden, der dann leichter ablaufen kann.Cleaning agents for hard surfaces, for example all-purpose kitchen cleaners and all-purpose bathroom cleaners, but also dishwashing detergents, hand washing-up liquids, glass cleaners, kitchen cleaners, bathroom and sanitary cleaners, toilet cleaners and disinfectant cleaners, often contain ingredients that make hard surfaces hydrophilic, which is why This means that water spreads better on such hard surfaces and water droplets form a film more quickly, which can then run off more easily.

In EP 2 138 560 A1 werden Pfropfcopolymere und ihre Verwendung in Mitteln zur Reinigung harter Oberflächen offenbart, unter anderem als Geschirrreiniger. Die in EP 2 138 560 A1 vorgeschlagenen Reinigungsmittel weisen jedoch noch eine gewisse Belagbildung (sog. "filming" oder "spotting") auf, vor allem auf Glas, Keramik und Edelstahl, was aus Sicht des Endanwenders kein optimales Ergebnis darstellt.In EP 2 138 560 A1 disclose graft copolymers and their use in agents for cleaning hard surfaces, including as dishwashers. In the EP 2 138 560 A1 However, the cleaning agents proposed still show a certain amount of deposit formation (so-called “filming” or “spotting”), especially on glass, ceramic and stainless steel, which is not an optimal result from the end user's point of view.

In WO 2015/197379 werden Formulierungen offenbart, die ein Pfropfcopolymer enthalten und weiterhin einen Builder, gewählt aus MGDA und GLDA und deren Salzen. Die offenbarten Formulierungen zeigen zwar eine gute Belagsinhibierung - insbesondere in Phosphat-freien Geschirrreinigern und insbesondere auf Glas. Die Formulierungen weisen jedoch für die Verwendung als Allzweckreiniger und als Klarspüler für Geschirr noch Verbesserungspotenzial auf.In WO 2015/197379 formulations are disclosed which contain a graft copolymer and furthermore a builder selected from MGDA and GLDA and their salts. The formulations disclosed show a good deposit inhibition - especially in phosphate-free dishwashing detergents and especially on glass. However, the formulations still have room for improvement for use as an all-purpose cleaner and as a rinse aid for dishes.

Es bestand also der Bedarf, Formulierungen bereit zu stellen, die insbesondere auf Glas-, Keramik- und Edelstahloberflächen zu einer deutlich stärker Hydrophilierung und damit einhergehend zu einer verbesserten Benetzung führen und somit zu einem verbesserten Glanzerhalt und möglcihst auch zu einer besseren Reinigungsleistung beitragen können.There was therefore a need to provide formulations which, in particular on glass, ceramic and stainless steel surfaces, lead to significantly more hydrophilicization and, as a result, to improved wetting and thus to improved gloss retention and, if possible, also to better cleaning performance.

Es bestand weiterhin die Aufgabe, ein Verfahren bereit zu stellen, durch das derartige Formulierungen hergestellt werden können.Another object was to provide a process by which formulations of this type can be produced.

Dem entsprechend wurden die eingangs definierten Formulierungen gefunden, im Rahmen der vorliegenden Erfindung auch erfindungsgemäße Formulierungen genannt.Accordingly, the formulations defined at the outset were found, also named formulations according to the invention in the context of the present invention.

Erfindungsgemäße Formulierungen können bei Zimmertemperatur, also bei 20°C, flüssig, fest, pastenförmig oder gelförmig sein. Vorzugsweise sind erfindungsgemäße Formulierungen bei Zimmertemperatur flüssig. Bei Zimmertemperatur feste erfindungsgemäße Formulierungen können wasserfrei sein oder Wasser enthalten, beispielsweise bis zu 20 Gew.-%, bevorzugt 0,1 bis 10 Gew.-% Wasser, bestimmbar beispielsweise durch Karl-Fischer-Titration oder durch Bestimmung des Trockenrückstands bei 80°C unter vermindertem Druck. Bei Zimmertemperatur feste erfindungsgemäße Formulierungen können beispielsweise in Form von Pulver, Granulat oder Tabletten vorliegen.Formulations according to the invention can be liquid, solid, paste-like or gel-like at room temperature, that is to say at 20 ° C. Formulations according to the invention are preferably liquid at room temperature. Formulations according to the invention which are solid at room temperature can be anhydrous or contain water, for example up to 20% by weight, preferably 0.1 to 10% by weight water, which can be determined for example by Karl Fischer titration or by determining the dry residue at 80 ° C under reduced pressure. Formulations according to the invention which are solid at room temperature can, for example, be in the form of powder, granules or tablets.

In einer anderen Ausführungsform sind erfindungsgemäße Formulierungen bei 20°C flüssig. Bei 20°C flüssige erfindungsgemäße Formulierungen können 10 bis 99,5 Gew.-% Wasser enthalten, bevorzugt 40 bis 99 Gew.-%, besonders bevorzugt 80 bis 99 Gew.-%. Auch in solchen Ausführungsformen kann der Wassergehalt durch Bestimmung des Trockenrückstands bei 80°C unter vermindertem Druck bestimmt werden. Bei Zimmertemperatur flüssige erfindungsgemäße Formulierungen können beispielsweise in Gelform, als Lösung, Suspension oder Emulsion vorliegen.In another embodiment, formulations according to the invention are liquid at 20 ° C. Formulations according to the invention which are liquid at 20 ° C. can contain 10 to 99.5% by weight of water, preferably 40 to 99% by weight, particularly preferably 80 to 99% by weight. In such embodiments, too, the water content can be determined by determining the dry residue at 80 ° C. under reduced pressure. Formulations according to the invention which are liquid at room temperature can, for example, be in gel form, as a solution, suspension or emulsion.

Erfindungsgemäße Formulierungen enthalten

  1. (A) mindestens ein nicht-ionisches Tensid, im Rahmen der vorliegenden Erfindung auch kurz als Verbindung (A), Tensid (A) oder nicht-ionisches Tensid (A) bezeichnet.
Contain formulations according to the invention
  1. (A) at least one non-ionic surfactant, also referred to for short in the context of the present invention as compound (A), surfactant (A) or non-ionic surfactant (A).

Bevorzugte nicht-ionische Tenside (A) sind alkoxylierte Alkohole und alkoxylierte Fettalkohole, Di- und Multiblockcopolymerisate von Ethylenoxid und Propylenoxid und Umsetzungsprodukte von Sorbitan mit Ethylenoxid oder Propylenoxid, Alkylpolyglykoside und sogenannte Aminoxide.Preferred nonionic surfactants (A) 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 polyglycosides and so-called amine oxides.

Bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind Verbindungen der allgemeinen Formel (II)

Figure imgb0002
in der die Variablen wie folgt definiert sind:

  • R3 gleich oder verschieden gewählt aus linearem C1-C10-Alkyl, bevorzugt Ethyl und besonders bevorzugt Methyl,
  • R4 gewählt aus C8-C22-Alkyl, beispielsweise n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 oder n-C18H37, oder Mischungen von mindestens zwei der vorstehenden Alkylresten,
  • R5 gewählt aus Wasserstoff und 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,
  • m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30.
Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (II)
Figure imgb0002
 in which the variables are defined as follows:
  • R 3, identically or differently, selected from linear C 1 -C 10 -alkyl, preferably ethyl and particularly preferably methyl,
  • R 4 is 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 , or mixtures of at least two of the above Alkyl radicals,
  • R 5 selected from hydrogen and C 1 -C 10 -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 or iso-decyl,
  • m and n range from zero to 300, with the sum of n and m being at least one. Preferably m is in the range from 1 to 100 and n in the range from 0 to 30.

Dabei kann es sich bei Verbindungen der allgemeinen Formel (II) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.Compounds of the general formula (II) can be block copolymers or random copolymers, block copolymers are preferred.

Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind Verbindungen der allgemeinen Formel (III)

Figure imgb0003
in der die Variablen wie folgt definiert sind:

R6
gewählt aus C6-C20-Alkyl, insbesondere n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37,
R7
gleich oder verschieden und gewählt aus linearem C1-C4-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl.
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.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds of the general formula (III)
Figure imgb0003
 in which the variables are defined as follows:
R 6
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 ,
R 7
identical or different and selected from linear C 1 -C 4 -alkyl, preferably identical in each case and ethyl and particularly preferably methyl.
a
a number in the range from 1 to 6,
b
is a number in the range from 4 to 20,
d
is a number in the range from 4 to 25.

Dabei kann es sich bei Verbindungen der allgemeinen Formel (III) um Blockcopolymere oder statistische Copolymere handeln, bevorzugt sind Blockcopolymere.Compounds of the general formula (III) can be block copolymers or random copolymers, block copolymers are preferred.

Andere bevorzugte Beispiele für alkoxylierte Alkohole und alkoxylierte Fettalkohole sind Hydroxymischether der allgemeinen Formel (IV)

        R8-CH(OH)-CH2-O-(AO)k-R9     (IV)

wobei die Variablen wie folgt gewählt werden:

R8
C4-C30-Alkyl, verzweigt oder unverzweigt, oder C4-C30-Alkenyl, verzweigt oder unverzweigt, mit mindestens einer C-C-Doppelbindung.
Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are hydroxy mixed ethers of the general formula (IV)

R 8 -CH (OH) -CH 2 -O- (AO) k -R 9 (IV)

where the variables are chosen as follows:
R 8
C 4 -C 30 -alkyl, branched or unbranched, or C 4 -C 30 -alkenyl, branched or unbranched, with at least one CC double bond.

Bevorzugt ist R8 gewählt aus C4-C30-Alkyl, verzweigt oder unverzweigt, besonders bevorzugt unverzweigtes C4-C30-Alkyl und ganz besonders bevorzugt n-C10-C12-Alkyl.

R9
C1-C30-Alkyl, verzweigt oder unverzweigt, oder, C2-C30-Alkenyl, verzweigt oder unverzweigt, mit mindestens einer C-C-Doppelbindung.
R 8 is preferably selected from C 4 -C 30 -alkyl, branched or unbranched, particularly preferably unbranched C 4 -C 30 -alkyl and very particularly preferably nC 10 -C 12 -alkyl.
R 9
C 1 -C 30 -alkyl, branched or unbranched, or, C 2 -C 30 -alkenyl, branched or unbranched, with at least one CC double bond.

Bevorzugt ist R9 gewählt aus C4-C30-Alkyl, verzweigt oder unverzweigt, besonders bevorzugt unverzweigtes C6-C20-Alkyl und ganz besonders bevorzugt n-C8-C11-Alkyl.

k
ist eine Zahl im Bereich von 1 bis 100, bevorzugt von 5 bis 60, besonders bevorzugt 10 bis 50 und ganz besonders bevorzugt 15 bis 40,
AO
ist gewählt aus Alkylenoxid, verschieden oder gleich und gewählt aus CH2-CH2-O, (CH2)3-O, (CH2)4-O, CH2CH(CH3)-O, CH(CH3)-CH2-O- und CH2CH(n-C3H7)-O. Bevorzugtes Beispiel von AO ist CH2-CH2-O (EO).
R 9 is preferably selected from C 4 -C 30 -alkyl, branched or unbranched, particularly preferably unbranched C 6 -C 20 -alkyl and very particularly preferably nC 8 -C 11 -alkyl.
k
is a number in the range from 1 to 100, preferably from 5 to 60, particularly preferably 10 to 50 and very particularly preferably 15 to 40,
AO
is selected from alkylene oxide, different or identical and selected from CH 2 -CH 2 -O, (CH 2 ) 3 -O, (CH 2 ) 4 -O, CH 2 CH (CH 3 ) -O, CH (CH 3 ) -CH 2 -O- and CH 2 CH (nC 3 H 7 ) -O. A preferred example of AO is CH 2 -CH 2 -O (EO).

In einer Ausführungsform der vorliegenden Erfindung wird (AO)k gewählt aus (CH2CH2O)k1, wobei k1 gewählt wird aus Zahlen im Bereich von 1 bis 50.In one embodiment of the present invention, (AO) k is selected from (CH 2 CH 2 O) k1 , where k1 is selected from numbers in the range from 1 to 50.

In einer Ausführungsform der vorliegenden Erfindung wird (AO)k gewählt aus -(CH2CH2O)k2-(CH2CH(CH3)-O)k3 und -(CH2CH2O)k2-(CH(CH3)CH2-O)x3, wobei k2 und k3 gleich oder verschieden sein können und aus Zahlen im Bereich von 1 bis 30 gewählt werden.In one embodiment of the present invention, (AO) k is selected from - (CH 2 CH 2 O) k2 - (CH 2 CH (CH 3 ) -O) k3 and - (CH 2 CH 2 O) k2 - (CH (CH 3 ) CH 2 -O) x3 , where k2 and k3 can be the same or different and are selected from numbers in the range from 1 to 30.

In einer Ausführungsform der vorliegenden Erfindung wird (AO)k gewählt aus -(CH2CH2O)k4, wobei k4 im Bereich von 10 bis 50 ist, AO ist EO, und R8 und R9 unabhängig voneinander aus C8-C14-Alkyl gewählt werden.In one embodiment of the present invention, (AO) k is selected from - (CH 2 CH 2 O) k4 , where k4 is in the range from 10 to 50, AO is EO, and R 8 and R 9 independently of one another from C 8 -C 14 alkyl can be selected.

Im Zusammenhang mit der vorliegenden Erfindung werden unter k bzw. k1, k2, k3 und k4 jeweils Mittelwerte verstanden, wobei das Zahlenmittel bevorzugt wird. Daher kann jede der Variablen k bzw. k1, k2, k3 oder k4 - so vorhanden - einen Bruch bedeuten. Ein bestimmtes Molekül kann natürlich immer nur eine ganze Zahl an AO-Einheiten tragen.In connection with the present invention, k or k1, k2, k3 and k4 are each mean values, the numerical mean being preferred. Therefore each of the variables k or k1, k2, k3 or k4 - if present - can mean a fraction. Of course, a particular molecule can only have a whole number of AO units.

Weitere Beispiele für geeignete nicht-ionische Tenside sind Verbindungen der allgemeinen Formel (V) und insbesondere der Formel (V a)

Figure imgb0004
Figure imgb0005
 wobei

  • R4 und AO wie vorstehend definiert sind und EO Ethylenoxid, also CH2CH2O, bedeutet, wobei die AO in Formel (VII) und (VII a) jeweils gleich oder verschieden sein können,
  • R8 gewählt aus C8-C18-Alkyl, linear oder verzweigt
  • A3O gewählt wird aus Propylenoxid und Butylenoxid,
  • w eine Zahl im Bereich von 15 bis 70, bevorzugt 30 bis 50 ist,
  • w1 und w3 Zahlen im Bereich von 1 bis 5 sind und
  • w2 eine Zahl im Bereich von 13 bis 35 ist.
Further examples of suitable non-ionic surfactants are compounds of the general formula (V) and in particular of the formula (V a)
Figure imgb0004
Figure imgb0005
 in which
  • R 4 and AO are as defined above and EO is ethylene oxide, i.e. CH 2 CH 2 O, where the AO in formula (VII) and (VII a) can each be the same or different,
  • R 8 selected from C 8 -C 18 -alkyl, linear or branched
  • A 3 O is chosen from propylene oxide and butylene oxide,
  • w is a number in the range from 15 to 70, preferably 30 to 50,
  • w1 and w3 are numbers ranging from 1 to 5 and
  • w2 is a number in the range 13 to 35.

Beispiele für Alkylpolyglykoside sind insbesondere Verbindungen der der Formel (VI)

Figure imgb0006
wobei

R10
gewählt ist aus C1-C10-Alkyl, insbesondere Ethyl, n-Propyl oder iso-Propyl, oder Wasserstoff
R11
ist -(CH2)2-R10 oder C1-C10-Alkyl
G1
ist gewählt aus Monosacchariden mit 4 bis 6 Kohlenstoffatomen, bevorzugt Glucose oder Xylose,
y
ist im Bereich von 1.1 bis 4, wobei y ein Durchschnittswert ist.
Examples of alkyl polyglycosides are, in particular, compounds of the formula (VI)
Figure imgb0006
 in which
R 10
is selected from C 1 -C 10 -alkyl, in particular ethyl, n-propyl or iso-propyl, or hydrogen
R 11
is - (CH 2 ) 2 -R 10 or C 1 -C 10 alkyl
G 1
is selected from monosaccharides with 4 to 6 carbon atoms, preferably glucose or xylose,
y
is in the range from 1.1 to 4, where y is an average value.

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 EP-A 0 851 023 und in DE-A 198 19 187 .Other suitable nonionic surfactants are selected from di- and multiblock copolymers, built up from ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are also suitable. An overview of other suitable nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187 .

Es können auch Gemische mehrerer verschiedener nicht-ionischer Tenside enthalten sein.It can also contain mixtures of several different nonionic surfactants.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Verbindung (A) aus Alkoholalkoxylaten und Alkylpolyglykosiden. Bevorzugt sind Alkoholalkoxylate.In a preferred embodiment of the present invention, compound (A) is selected from alcohol alkoxylates and alkyl polyglycosides. Alcohol alkoxylates are preferred.

Erfindungsgemäße Formulierungen enthalten kein oder nur wenig MGDA und dessen Salze. Erfindungsgemäße Formulierungen enthalten kein oder nur wenig GLDA und seine Salze. Erfindungsgemäße Formulierungen enthalten kein oder nur wenig Citronensäure und ihre Salze. Spezifisch enthalten erfindungsgemäße Formulierungen
(C) null bis maximal 0,5, bevorzugt null bis 0,1 Gew.-% Methylglycindiessigsäure (MGDA) und Glutaminsäurediessigsäure (GLDA) und Alkalimetallsalze von MGDA und GLDA. Dabei ist es im Rahmen der vorliegenden Erfindung nicht erheblich, ob MGDA bzw. GLDA bzw. die entsprechenden Salze in enantiomerenreiner oder racemischer Form vorliegen oder als enantiomerenangereicherte Mischung.Formulations according to the invention contain little or no MGDA and its salts. Formulations according to the invention contain little or no GLDA and its salts. Formulations according to the invention contain little or no citric acid and its salts. Specifically, formulations according to the invention contain
(C) zero to a maximum of 0.5, preferably zero to 0.1% by weight of methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and alkali metal salts of MGDA and GLDA. In the context of the present invention, it is not important whether MGDA or GLDA or the corresponding salts are present in enantiomerically pure or racemic form or as an enantiomerically enriched mixture.

Außerdem enthalten erfindungsgemäße Formulierungen von null bis 0,5 Gew.-% Citronensäure und Alkalimetallsalz von Citronensäure.In addition, formulations according to the invention contain from zero to 0.5% by weight of citric acid and the alkali metal salt of citric acid.

GLDA und MGDA sowie ihre Alkalimetallsalze können als Hydrate vorliegen. Citronensäure selbst und Salze der Citronensäure liegen in der Regel als Hydrate vor. Beispielsweise liegt Natriumzitrat unter Normalbedingungen in der Regel als Dihydrat und Kaliumzitrat als Monohydrat vor. Wenn nicht ausdrücklich anders angegeben, beziehen sich im Rahmen der vorliegenden Erfindung Mengenangaben im Zusammenhang mit Verbindung (A) stets auf den Wirkstoff, also ohne Berücksichtigung von Hydrat. Wenn nicht ausdrücklich anders angegeben, beziehen sich im Rahmen der vorliegenden Erfindung Mengenangaben im Zusammenhang mit MGDA bzw. GLDA bzw. Citronensäure bzw. deren Alkalimetallsalze stets auf den Wirkstoff, also ohne Berücksichtigung von Hydrat.GLDA and MGDA and their alkali metal salts can be present as hydrates. Citric acid itself and salts of citric acid are usually in the form of hydrates. For example, sodium citrate is usually present as a dihydrate and potassium citrate as a monohydrate under normal conditions. Unless expressly stated otherwise, refer in the context of the present Invention, quantitative data in connection with compound (A) always refer to the active ingredient, ie without taking hydrate into account. Unless expressly stated otherwise, in the context of the present invention, quantitative data in connection with MGDA or GLDA or citric acid or its alkali metal salts always relate to the active ingredient, ie without taking hydrate into account.

Erfindungsgemäße Formulierungen enthalten
(B) mindestens ein Pfropfcopolymer, das im Rahmen der vorliegenden Erfindung auch Pfropfcopolymer (B) oder erfindungsgemäße Pfropfcopolymer (B) genannt wird und das aufgebaut ist aus

  1. (a) mindestens einer Pfropfgrundlage, kurz Pfropfgrundlage (a) genannt, die gewählt ist aus nicht-ionischen Monosacchariden, Disacchariden, Oligosacchariden und Polysacchariden,
    und Seitenketten, erhältlich durch Aufpfropfen von
  2. (b) mindestens einer ethylenisch ungesättigten Mono- oder Dicarbonsäure, kurz Monocarbonsäure (b) bzw. Dicarbonsäure (b) genannt, und
  3. (c) mindestens einer Verbindung der allgemeinen Formel (I), kurz Monomer (c) oder Verbindung (c) oder Verbindung (I) genannt,
    Figure imgb0007
     wobei die Variablen wie folgt definiert sind:
    • R1 ist gewählt aus Methyl und Wasserstoff,
    • A1 ist gewählt aus C2-C4-Alkylen,
    • R2 sind gleich oder verschieden und gewählt aus C1-C4-Alkyl,
    • X- ist gewählt aus Halogenid, Mono-C1-C4-Alkylsulfat und Sulfat.
Contain formulations according to the invention
(B) at least one graft copolymer, which in the context of the present invention is also called graft copolymer (B) or graft copolymer (B) according to the invention and which is composed of
  1. (a) at least one graft base, called graft base (a) for short, which is selected from non-ionic monosaccharides, disaccharides, oligosaccharides and polysaccharides,
    and side chains obtainable by grafting
  2. (b) at least one ethylenically unsaturated mono- or dicarboxylic acid, called monocarboxylic acid (b) or dicarboxylic acid (b) for short, and
  3. (c) at least one compound of the general formula (I), called monomer (c) or compound (c) or compound (I) for short,
    Figure imgb0007
     where the variables are defined as follows:
    • R 1 is selected from methyl and hydrogen,
    • A 1 is selected from C 2 -C 4 alkylene,
    • R 2 are identical or different and are selected from C 1 -C 4 -alkyl,
    • X- is selected from halide, mono-C 1 -C 4 -alkyl sulfate and sulfate.

Als Pfropfgrundlage (a) geeignete nicht-ionische Monosaccharide kann man beispielsweise Aldopentosen, Pentulosen (Ketopentosen), Aldohexosen und Hexulosen (Ketohexosen) wählen. Geeignete Aldopentosen sind z.B. D-Ribose, D-Xylose und L-Arabinose. Als Aldohexosen seien D-Glucose, D-Mannose und D-Galactose genannt; als Beispiele von Hexulosen (Ketohexosen) sind vor allem D-Fructose und D-Sorbose zu nennen.Suitable nonionic monosaccharides as the graft base (a) can be selected, for example, from aldopentoses, pentuloses (ketopentoses), aldohexoses and hexuloses (ketohexoses). Suitable aldopentoses are e.g. D-ribose, D-xylose and L-arabinose. D-glucose, D-mannose and D-galactose may be mentioned as aldohexoses; Examples of hexuloses (ketohexoses) are especially D-fructose and D-sorbose.

Im Rahmen der vorliegenden Erfindung sollen auch Desoxyzucker wie beispielsweise L-Fucose und L-Rhamnose zu nicht-ionischen Monosacchariden gezählt werden.In the context of the present invention, deoxy sugars such as L-fucose and L-rhamnose are also to be counted among non-ionic monosaccharides.

Als Beispiele für nicht-ionische Disaccharide seien beispielsweise Cellobiose, Lactose, Maltose und Saccharose genannt.Examples of non-ionic disaccharides include cellobiose, lactose, maltose and sucrose.

Als nicht-ionische Oligosaccharide seien im Rahmen der vorliegenden Erfindung nicht-ionische Kohlenhydrate mit drei bis zehn nicht-ionischen Monosaccharideinheiten pro Molekül bezeichnet, beispielsweise Glycane. Als nicht-ionische Polysaccharide werden im Rahmen der vorliegenden Erfindung nicht-ionische Kohlenhydrate mit mehr als zehn nicht-ionischen Monosaccharideinheiten pro Molekül bezeichnet. Nicht-ionische Oligo- und Polysaccharide können beispielsweise linear, cyclisch oder verzweigt sein.In the context of the present invention, nonionic carbohydrates with three to ten nonionic monosaccharide units per molecule, for example glycans, are referred to as nonionic oligosaccharides. In the context of the present invention, non-ionic polysaccharides are non-ionic carbohydrates with more than ten non-ionic monosaccharide units per molecule. Nonionic oligo- and polysaccharides can be linear, cyclic or branched, for example.

Als nicht-ionische Polysaccharide beispielhaft zu nennen sind Biopolymere wie Stärke und Glycogen sowie Cellulose und Dextran. Weiterhin zu nennen sind Inulin als Polykondensat der D-Fructose (Fructane) und Chitin. Weitere Beispiele von nicht-ionischen Polysacchariden sind nicht-ionische Stärkeabbauprodukte, beispielsweise Produkte, die man durch enzymatischen oder sogenannten chemischen Abbau von Stärke erhalten kann. Ein Beispiel für den sogenannten chemischen Abbau von Stärke ist die säurekatalysierte Hydrolyse.Examples of non-ionic polysaccharides that should be mentioned are biopolymers such as starch and glycogen as well as cellulose and dextran. Also to be mentioned are inulin as a polycondensate of D-fructose (fructans) and chitin. Further examples of non-ionic polysaccharides are non-ionic starch degradation products, for example products which can be obtained by enzymatic or so-called chemical degradation of starch. An example of the so-called chemical breakdown of starch is acid-catalyzed hydrolysis.

Bevorzugte Beispiele für nicht-ionische Stärkeabbauprodukte sind Maltodextrine. Unter Maltodextrin werden im Rahmen der vorliegenden Erfindung Gemische aus Monomeren, Dimeren, Oligomeren und Polymeren der Glucose gefasst. Je nach Hydrolysegrad unterscheidet sich die prozentuale Zusammensetzung. Diese wird durch das Dextrose-Äquivalent beschrieben, das bei Maltodextrin zwischen 3 und 40 liegt.Preferred examples of non-ionic starch degradation products are maltodextrins. In the context of the present invention, maltodextrin is understood to mean mixtures of monomers, dimers, oligomers and polymers of glucose. The percentage composition differs depending on the degree of hydrolysis. This is described by the dextrose equivalent, which is between 3 and 40 for maltodextrin.

Bevorzugt wählt man Pfropfgrundlage (a) aus nicht-ionischen Polysacchariden, insbesondere aus Stärke, die vorzugsweise nicht chemisch modifiziert ist, beispielsweise deren Hydroxylgruppen vorzugsweise weder verestert noch verethert sind. In einer Ausführungsform der vorliegenden Erfindung wählt man Stärke aus solchen nicht-ionischen Polysacchariden, die im Bereich von 20 bis 30 Gew.-% Amylose und im Bereich von 70 bis 80% Amylopektin aufweisen. Beispiele sind Maisstärke, Reisstärke, Kartoffelstärke und Weizenstärke.The graft base (a) is preferably chosen from nonionic polysaccharides, in particular from starch, which is preferably not chemically modified, for example whose hydroxyl groups are preferably neither esterified nor etherified. In one embodiment of the present invention, starch is selected from those nonionic polysaccharides which have in the range from 20 to 30% by weight amylose and in the range from 70 to 80% amylopectin. Examples are corn starch, rice starch, potato starch and wheat starch.

Auf die Pfropfgrundlage (a) sind Seitenketten aufgepfropft. Pro Molekül von Pfropfcopolymer (B) können vorzugsweise im Mittel eine bis zehn Seitenketten aufgepfropft sein. Vorzugsweise ist dabei eine Seitenkette mit dem anomeren C-Atom eines Monosaccharids oder mit einem anomeren C-Atom des Kettenendes eines Oligo- oder Polysaccharids verknüpft. Die Zahl der Seitenketten ist durch die Zahl der C-Atome mit Hydroxyl-Gruppen der betreffenden Pfropfgrundlage (a) nach oben begrenzt.Side chains are grafted onto the graft base (a). An average of one to ten side chains can preferably be grafted on per molecule of graft copolymer (B). A side chain is preferably linked to the anomeric carbon atom of a monosaccharide or to an anomeric carbon atom of the chain end of an oligo- or polysaccharide. The number of side chains is limited by the number of carbon atoms with hydroxyl groups of the graft base (a) in question.

Beispiele für Monocarbonsäuren (b) sind ethylenisch ungesättigte C3-C10-Monocarbonsäuren und deren Alkalimetall- oder Ammoniumsalze, insbesondere die Kalium- und die Natriumsalze. Bevorzugte Monocarbonsäuren (b) sind die Acrylsäure und die Methacrylsäure sowie Natrium(meth)acrylat. Auch Mischungen von ethylenisch ungesättigten C3-C10 Monocarbonsäuren und insbesondere Mischungen von Acryl- und Methacrylsäure sind bevorzugte Komponenten (b).Examples of monocarboxylic acids (b) are ethylenically unsaturated C 3 -C 10 monocarboxylic acids and their alkali metal or ammonium salts, in particular the potassium and sodium salts. Preferred monocarboxylic acids (b) are acrylic acid and methacrylic acid and sodium (meth) acrylate. Mixtures of ethylenically unsaturated C 3 -C 10 monocarboxylic acids and in particular mixtures of acrylic and methacrylic acid are also preferred components (b).

Beispiele für Dicarbonsäuren (b) sind ethylenisch ungesättigte C4-C10-Dicarbonsäuren und deren Mono- und insbesondere Dialkalimetall- oder Ammoniumsalze, insbesondere die Dikalium- und die Dinatriumsalze, sowie Anhydride von ethylenisch ungesättigten C4-C10-Dicarbonsäuren. Bevorzugte Dicarbonsäuren (b) sind die Maleinsäure, Fumarsäure, Itaconsäure sowie Maleinsäureanhydrid und Itaconsäureanhydrid.Examples of dicarboxylic acids (b) are ethylenically unsaturated C 4 -C 10 dicarboxylic acids and their mono- and especially dialkali metal or ammonium salts, in particular the dipotassium and disodium salts, and anhydrides of ethylenically unsaturated C 4 -C 10 dicarboxylic acids. Preferred dicarboxylic acids (b) are maleic acid, fumaric acid, itaconic acid and maleic anhydride and itaconic anhydride.

In einer Ausführungsform enthält Pfropfcopolymer (B) in mindestens einer Seitenkette neben Monomer (c) mindestens eine Monocarbonsäure (b) und mindestens eine Dicarbonsäure (b). In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthält Pfropfcopolymer (B) in den Seitenketten neben Monomer (c) ausschließlich Monocarbonsäure (b), aber keine Dicarbonsäure (b) einpolymerisiert.In one embodiment, graft copolymer (B) contains at least one side chain in addition to monomer (c) at least one monocarboxylic acid (b) and at least one dicarboxylic acid (b). In a preferred embodiment of the present invention, graft copolymer (B) contains, in addition to monomer (c), exclusively monocarboxylic acid (b) in the side chains, but no dicarboxylic acid (b) in copolymerized form.

Monomere (c) sind ethylenisch ungesättigte N-haltige Verbindungen mit permanenter kationischer Ladung.

Figure imgb0008
wobei die Variablen wie folgt definiert sind:

  • R1 ist gewählt aus Methyl und Wasserstoff,
  • A1 ist gewählt aus C2-C4-Alkylen, beispielsweise -CH2-CH2-, CH2-CH(CH3)-, -(CH2)3-, -(CH2)4-, bevorzugt sind -CH2-CH2- und -(CH2)3-,
  • R2 sind verschieden oder vorzugsweise gleich und gewählt aus C1-C4-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, n-Butyl, iso-Propyl, iso-Butyl, sec.-Butyl, tert.-Butyl, bevorzugt sind mindestens zwei R2 gleich und jeweils Methyl, und die dritte Gruppe R2 ist Ethyl, n-Propyl oder n-Butyl, oder zwei R2 sind gleich und jeweils Ethyl, und die dritte Gruppe R2 ist Methyl, n-Propyl oder n-Butyl. Besonders bevorzugt sind alle drei R2 jeweils gleich und gewählt aus Methyl.
  • X- ist gewählt aus Halogenid, beispielsweise lodid, Bromid und insbesondere Chlorid, weiterhin aus Mono-C1-C4-Alkylsulfat und Sulfat. Beispiele für Mono-C1-C4-Alkylsulfat sind Methylsulfat, Ethylsulfat, iso-Propylsulfat und n-Butylsulfat, bevorzugt sind Methylsulfat und Ethylsulfat. Wenn man X- als Sulfat wählt, so steht X- für ein halbes Äquivalent Sulfat.
Monomers (c) are ethylenically unsaturated N-containing compounds with a permanent cationic charge.
Figure imgb0008
 where the variables are defined as follows:
  • R 1 is selected from methyl and hydrogen,
  • A 1 is selected from C 2 -C 4 -alkylene, for example -CH 2 -CH 2 -, CH 2 -CH (CH 3 ) -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, are preferred -CH 2 -CH 2 - and - (CH 2 ) 3 -,
  • R 2 are different or preferably the same and are selected from C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, n-butyl, iso-propyl, iso-butyl, sec-butyl, tert-butyl, preferably at least two R 2 are the same and each methyl, and the third group R 2 is ethyl, n-propyl or n-butyl, or two R 2 are the same and each are ethyl, and the third group R 2 is methyl, n-propyl or n-butyl. All three R 2 are particularly preferably each identical and are selected from methyl.
  • X- is selected from halide, for example iodide, bromide and, in particular, chloride, and also from mono-C 1 -C 4 -alkyl sulfate and sulfate. Examples of mono-C 1 -C 4 -alkyl sulfate are methyl sulfate, Ethyl sulphate, iso-propyl sulphate and n-butyl sulphate, methyl sulphate and ethyl sulphate are preferred. If you choose X- as sulfate, then X- stands for half an equivalent of sulfate.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind in Monomer (c) die Variablen wie folgt gewählt:

  • R1 ist Wasserstoff oder Methyl,
  • R2 sind gleich und jeweils Methyl,
  • A1 ist CH2CH2, und
  • X- ist Chlorid.
In a preferred embodiment of the present invention, the variables in monomer (c) are selected as follows:
  • R 1 is hydrogen or methyl,
  • R 2 are the same and are each methyl,
  • A 1 is CH 2 CH 2 , and
  • X- is chloride.

In einer Ausführungsform der vorliegenden Erfindung ist Monomer (c) gewählt aus

Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
 In one embodiment of the present invention, monomer (c) is selected from
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012

Pfropfcopolymer (B) kann in einer oder mehreren Seitenketten mindestens ein weiteres Comonomer (d) einpolymerisiert enthalten, beispielsweise Hydroxyalkylester wie 2-Hydroxyethyl-(meth)acrylat oder 3-Hydroxypropyl(meth)acrylat, oder Ester von alkoxylierten Fettalkoholen, oder Sulfonsäuregruppen-haltige Comonomere, beispielsweise 2-Acrylamido-2-methylpropansulfonsäure (AMPS) und ihre Alkalimetallsalze.Graft copolymer (B) can contain at least one further comonomer (d) in copolymerized form in one or more side chains, for example hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, or esters of alkoxylated fatty alcohols, or comonomers containing sulfonic acid groups, for example 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts.

Vorzugsweise enthält Pfropfcopolymer (B) außer Monomer (c) und Monocarbonsäure (b) bzw. Dicarbonsäure (b) keine weiteren Comonomere (d) in einer oder mehreren Seitenketten.Apart from monomer (c) and monocarboxylic acid (b) or dicarboxylic acid (b), graft copolymer (B) preferably contains no further comonomers (d) in one or more side chains.

In einer Ausführungsform der vorliegenden Erfindung ist der Anteil von Pfropfgrundlage (a) in Pfropfcopolymer (B) im Bereich von 40 bis 95 Gew.-%, vorzugsweise von 50 bis 90 Gew.-%, jeweils bezogen auf gesamtes Pfropfcopolymer (B).In one embodiment of the present invention, the proportion of graft base (a) in graft copolymer (B) is in the range from 40 to 95% by weight, preferably from 50 to 90% by weight, based in each case on the total graft copolymer (B).

In einer Ausführungsform der vorliegenden Erfindung ist der Anteil von Monocarbonsäure (b) bzw. Dicarbonsäure (b) im Bereich von 2 bis 40 Gew.-%, vorzugsweise von 5 bis 30 Gew.-% und insbesondere von 5 bis 25 Gew.-%, jeweils bezogen auf gesamtes Pfropfcopolymer (B).In one embodiment of the present invention, the proportion of monocarboxylic acid (b) or dicarboxylic acid (b) is in the range from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 5 to 25% by weight , in each case based on the total graft copolymer (B).

Monomer bzw. Monomere (c) ist bzw. sind in Mengen von 5 bis 50 Gew.-%, vorzugsweise von 5 bis 40 Gew.-% und besonders bevorzugt von 5 bis 30 Gew.-% einpolymerisiert, jeweils bezogen auf gesamtes Pfropfcopolymer (B).Monomer or monomers (c) is or are polymerized in amounts of 5 to 50% by weight, preferably 5 to 40% by weight and particularly preferably 5 to 30% by weight, each based on the total graft copolymer ( B).

Es ist bevorzugt, wenn Pfropfcopolymer (B) mehr Monocarbonsäure (b) als Monomer (c) einpolymerisiert enthält, und zwar auf die molaren Anteile bezogen, beispielsweise im Bereich von 1,1:1 bis 5:1, bevorzugt 2:1 bis 4:1.It is preferred if graft copolymer (B) contains more monocarboxylic acid (b) than monomer (c) in copolymerized form, based on the molar proportions, for example in the range from 1.1: 1 to 5: 1, preferably 2: 1 to 4 :1.

In einer Ausführungsform der vorliegenden Erfindung ist das mittlere Molekulargewicht (Mw) von Pfropfcopolymer (B) im Bereich von 1.500 bis 200.000 g/mol, vorzugsweise von 2.000 bis 150.000 und insbesondere im Bereich von 3.000 bis 100.000 g/mol. Das mittlere Molekulargewicht Mw misst man vorzugsweise durch Gelpermeationschromatographie in wässriger KCl/Ameisensäure-Lösung.In one embodiment of the present invention, the average molecular weight (M w ) of graft copolymer (B) is in the range from 1,500 to 200,000 g / mol, preferably from 2,000 to 150,000 and in particular in the range from 3,000 to 100,000 g / mol. The average molecular weight M w is preferably measured by gel permeation chromatography in an aqueous KCl / formic acid solution.

Pfropfcopolymer (B) kann man vorzugsweise als wässrige Lösung erhalten, aus der man es isolieren kann, z. B. durch Sprühtrocknung, Sprühgranulierung oder Gefriertrocknung. Wahlweise kann man Lösung von Pfropfcopolymer (B) oder getrocknetes Pfropfcopolymer (B) zur Herstellung der erfindungsgemäßen Formulierungen verwenden.Graft copolymer (B) can preferably be obtained as an aqueous solution from which it can be isolated, e.g. B. by spray drying, spray granulation or freeze drying. Alternatively, a solution of graft copolymer (B) or dried graft copolymer (B) can be used for the preparation of the formulations according to the invention.

Es ist bevorzugt, Pfropfcopolymer (B) durch mindestens ein Biozid zu stabilisieren. Beispiele für geeignete Biozide sind Isothiazolinone, beispielsweise 1,2-Benzisothiazolin-3-on ("BIT"), Octylisothiazolinon ("OIT"), Dichloroktylisothiazolinon ("DCOIT"), 2-Methyl-2H-isothiazolin-3-on ("MIT") und 5-Chlor-2-methyl-2H-isothiazolin-3-one("CIT"), Phenoxyethanol, Alkylparabene wie Methylparaben, Ethylparaben, Propylparaben, Benzoesäure und ihre Salze wie z.B. Natriumbenzoat, Benzylalkohol, Alkalimetallsorbate wie z.B. Natriumsorbat, und gegebenenfalls substituierte Hydantoine wie z.B. 1,3-Bis(hydroxymethyl)-5,5-dimethylhydantoin (DMDM-Hydantoin).It is preferred to stabilize the graft copolymer (B) with at least one biocide. Examples of suitable biocides are isothiazolinones, for example 1,2-benzisothiazolin-3-one ("BIT"), octylisothiazolinone ("OIT"), dichloroctylisothiazolinone ("DCOIT"), 2-methyl-2 H -isothiazolin-3-one ( "MIT") and 5-chloro-2-methyl-2 H -isothiazolin-3-one ("CIT"), phenoxyethanol, alkyl parabens such as methyl paraben, ethyl paraben, propyl paraben, benzoic acid and its salts such as sodium benzoate, benzyl alcohol, alkali metal sorbates such as Sodium sorbate and optionally substituted hydantoins such as, for example, 1,3-bis (hydroxymethyl) -5,5-dimethylhydantoin (DMDM hydantoin).

Weitere Beispiele sind 1,2-Dibrom-2, 4-dicyanobutan, Iodo-2-propynyl-butyl-carbamat, lod und lodophore.Further examples are 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine and iodophores.

In einer 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 vorliegenden 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 one embodiment of the present invention, the formulation according to the invention is free from phosphates and polyphosphates, hydrogen phosphates also being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate. In connection with phosphates and polyphosphates, “free of” should be understood in the context of the present invention that the total content of phosphate and polyphosphate is in the range from 10 ppm to 0.2% by weight, determined by gravimetry.

In einer Ausführungsform der vorliegenden Erfindung ist erfindungsgemäße Formulierung frei von solchen Schwermetallverbindungen, die nicht als Bleichkatalysatoren wirken, insbesondere von Verbindungen des Eisens. 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, bevorzugt 1 bis 30 ppm, bestimmt nach der Leach-Methode.In one embodiment of the present invention, the formulation according to the invention is free from those heavy metal compounds which do not act as bleach catalysts, in particular from compounds of iron. In connection with heavy metal compounds in the context of the present invention, “free of” is to be understood as meaning that the total content of heavy metal compounds that do not act as bleach catalysts is in the range from 0 to 100 ppm, preferably 1 to 30 ppm, determined according to the Leach method.

Als "Schwermetalle" gelten im Rahmen der vorliegenden Erfindung alle Metalle mit einer spezifischen Dichte von mindestens 6 g/cm3, mit der Ausnahme von Zink und Wismut. Insbesondere gelten als Schwermetalle Edelmetalle sowie Eisen, Kupfer, Blei, Zinn, Nickel, Cadmium und Chrom.In the context of the present invention, "heavy metals" are all metals with a specific density of at least 6 g / cm 3 , with the exception of zinc and bismuth. In particular, heavy metals are precious metals such as iron, copper, lead, tin, nickel, cadmium and chromium.

In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße FormulierungIn one embodiment of the present invention, formulation according to the invention contains

insgesamt im Bereich von 20 bis 99 Gew.-% Verbindung (A), bevorzugt 40 bis 98 Gew.-%, besonders bevorzugt 50 bis 95 Gew.-%, und
insgesamt im Bereich von 1 bis 40 Gew.-% Pfropfcopolymer (B), bevorzugt 3 bis 30 Gew.-%, besonders bevorzugt 5 bis 20 Gew.-%,
bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung.in total in the range from 20 to 99% by weight of compound (A), preferably 40 to 98% by weight, particularly preferably 50 to 95% by weight, and
in total in the range from 1 to 40% by weight of graft copolymer (B), preferably 3 to 30% by weight, particularly preferably 5 to 20% by weight,
based in each case on the solids content of the formulation in question.

Für flüssige und feste Formulierungen Formulierung ist das Gewichtsverhältnis von Verbindung (A) zu Pfropfcopolymer (B) vorzugsweise im Bereich von 1:2 bis 20:1.For liquid and solid formulations, the weight ratio of compound (A) to graft copolymer (B) is preferably in the range from 1: 2 to 20: 1.

In einer Ausführung enthalten erfindungsgemäße flüssige FormulierungenIn one embodiment, liquid formulations according to the invention contain

insgesamt im Bereich von 20 bis 99,9 Gew.-% Verbindung (A), bevorzugt 40 bis 98 Gew.-%, besonders bevorzugt 50 bis 95 Gew.-%, und
insgesamt im Bereich von 0,01 bis 40 Gew.-% Pfropfcopolymer (B), bevorzugt 3 bis 30 Gew.-%, besonders bevorzugt 5 bis 20 Gew.-%,
bezogen jeweils auf die betreffende erfindungsgemäße wässrige Formulierung.in total in the range from 20 to 99.9% by weight of compound (A), preferably 40 to 98% by weight, particularly preferably 50 to 95% by weight, and
in total in the range from 0.01 to 40% by weight of graft copolymer (B), preferably 3 to 30% by weight, particularly preferably 5 to 20% by weight,
based in each case on the aqueous formulation according to the invention in question.

Erfindungsgemäße Formulierungen können frei sein von Bleichmitteln, beispielsweise frei von anorganischen Peroxidverbindungen oder Chlorbleichmitteln wie Natriumhypochlorit. Unter frei von anorganischen Peroxidverbindungen oder Chlorbleichmitteln soll dabei verstanden werden, dass derartige erfindungsgemäße Formulierungen insgesamt 0,01 Gew.-% oder weniger anorganische Peroxidverbindung und Chlorbleichmittel enthalten, bezogen jeweils auf Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.Formulations according to the invention can be free from bleaching agents, for example free from inorganic peroxide compounds or chlorine bleaching agents such as sodium hypochlorite. Free from inorganic peroxide compounds or chlorine bleaching agents should be understood to mean that such formulations according to the invention contain a total of 0.01% by weight or less of inorganic peroxide compounds and chlorine bleaching agents, based in each case on the solids content of the formulation according to the invention in question.

In einer anderen Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße Formulierung
(D) mindestens eine anorganische Peroxidverbindung, im Rahmen der vorliegenden Erfindung kurz auch als Peroxid (D) bezeichnet wird. Peroxid (D) ist gewählt aus Wasserstoffperoxid, Natriumperoxodisulfat, Natriumperborat und Natriumpercarbonat, bevorzugt ist Natriumpercarbonat. In festen erfindungsgemäßen Formulierungen ist Natriumpercarbonat bevorzugt, und in erfindungsgemäßen flüssigen Formulierungen ist Wasserstoffperoxid bevorzugt.In another embodiment of the present invention, formulation according to the invention contains
(D) at least one inorganic peroxide compound, also referred to for short in the context of the present invention as peroxide (D). Peroxide (D) is selected from hydrogen peroxide, sodium peroxodisulfate, sodium perborate and sodium percarbonate, sodium percarbonate is preferred. Sodium percarbonate is preferred in solid formulations according to the invention and hydrogen peroxide is preferred in liquid formulations according to the invention.

Festes Peroxid (D) kann wasserfrei oder vorzugsweise wasserhaltig sein. Beispiele für wasserhaltiges Natriumperborat ist Na2[B(OH)2(O2)]2), manchmal auch als NaBO2·O2·3H2O geschrieben wird. Beispiel für wasserhaltiges Natriumpercarbonat ist 2 Na2CO3·3 H2O2. Besonders bevorzugt wählt man festes Peroxid (D) aus wasserhaltigen Percarbonaten.Solid peroxide (D) can be anhydrous or preferably contain water. Examples of hydrous sodium perborate are Na 2 [B (OH) 2 (O 2 )] 2 ), sometimes also written as NaBO 2 · O 2 · 3H 2 O. An example of sodium percarbonate containing water is 2 Na 2 CO 3 · 3 H 2 O 2 . Solid peroxide (D) is particularly preferably chosen from hydrous percarbonates.

Percarbonate und insbesondere Natriumpercarbonat setzt man vorzugsweise in beschichteter Form ein. Die Beschichtung kann anorganischer oder organischer Natur sein. Beispiele für Beschichtungsmittel sind Glyzerin, Natriumsulfat, Kieselgel, Natriumsilikat, Natriumcarbonat und Kombination von mindestens zwei der vorgehenden Beschichtungsmittel, beispielsweise Natriumcarbonat und Natriumsulfat.Percarbonates and in particular sodium percarbonate are preferably used in coated form. The coating can be of an inorganic or organic nature. Examples of coating agents are glycerol, sodium sulfate, silica gel, sodium silicate, sodium carbonate and combinations of at least two of the above coating agents, for example sodium carbonate and sodium sulfate.

Bevorzugt enthalten erfindungsgemäße feste Formulierungen im Bereich von 1 bis 30 Gew.-% Peroxid (D), bevorzugt 2 bis 15 Gew.-%, besonders bevorzugt 3 bis 12 Gew.-%, bezogen auf Feststoffgehalt der betreffenden festen Formulierung.Solid formulations according to the invention preferably contain in the range from 1 to 30% by weight peroxide (D), preferably 2 to 15% by weight, particularly preferably 3 to 12% by weight, based on the solids content of the solid formulation in question.

Bevorzugt enthalten erfindungsgemäße flüssige Formulierungen im Bereich von 1 bis 30 Gew.-% Peroxid (D), bevorzugt 2 bis 15 Gew.-%, besonders bevorzugt 3 bis 12 Gew.-%, bezogen jeweils auf Feststoffgehalt der betreffenden Formulierung. Für den Fall der flüssigen erfindungsgemäßen Formulierung handelt es sich bei Peroxid (D) bevorzugt um Wasserstoffperoxid.Liquid formulations according to the invention preferably contain in the range from 1 to 30% by weight of peroxide (D), preferably 2 to 15% by weight, particularly preferably 3 to 12% by weight, based in each case on the solids content of the formulation in question. In the case of the liquid formulation according to the invention, peroxide (D) is preferably hydrogen peroxide.

Erfindungsgemäße Formulierungen, die mindestens ein Peroxid (D) enthalten, sind bei Zimmertemperatur vorzugsweise flüssig.Formulations according to the invention which contain at least one peroxide (D) are preferably liquid at room temperature.

In einer anderen Ausführungsform enthält erfindungsgemäße Formulierung
(D) mindestens ein Chlor-haltiges Bleichmittel, welches im Rahmen der vorliegenden Erfindung kurz auch als Chlorbleichmittel (D) bezeichnet wird. Bei Chlorbleichmittel (D) handelt es sich vorzugsweise um Natriumhypochlorit.In another embodiment, formulation according to the invention contains
(D) at least one chlorine-containing bleach, which in the context of the present invention is also referred to for short as chlorine bleach (D). Chlorine bleach (D) is preferably sodium hypochlorite.

Chlorbleichmittel-(D)-haltige erfindungsgemäße Formulierungen sind bei Zimmertemperatur vorzugsweise flüssig.Chlorine bleach (D) -containing formulations according to the invention are preferably liquid at room temperature.

Bevorzugt enthält erfindungsgemäße Formulierung im Bereich von 0,1 bis 30 Gew.-% Chlorbleichmittel (D), bevorzugt 0,5 bis 15 Gew.-%, besonders bevorzugt 1 bis 12 Gew.-%, bezogen auf Feststoffgehalt der betreffenden flüssigen Formulierung.The formulation according to the invention preferably contains in the range from 0.1 to 30% by weight of chlorine bleach (D), preferably 0.5 to 15% by weight, particularly preferably 1 to 12% by weight, based on the solids content of the liquid formulation in question.

Erfindungsgemäße Formulierungen können einen oder mehrere weitere Inhaltsstoffe (E) enthalten. Inhaltsstoffe (E) sind von Verbindung (A), Pfropfcopolymer (B) und Peroxid (D) bzw. Chlorbleichmittel (D) verschieden.Formulations according to the invention can contain one or more further ingredients (E). Ingredients (E) are different from compound (A), graft copolymer (B) and peroxide (D) or chlorine bleach (D).

Erfindungsgemäße Formulierungen können einen oder mehrere weitere Inhaltsstoffe (E) aufweisen, beispielsweise ein oder mehrere anionische oder zwitterionische Tenside, ein oder mehrere Enzyme, einen oder mehrere Enzymstabilisatoren, einen oder mehrere Alkaliträger, eine oder mehrere Säuren, 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 Verdickungsmittel, ein oder mehrere organische Lösungsmittel, ein oder mehrere Tablettierhilfsmittel, ein oder mehrere Disintegrationsmittel, auch Tablettensprengmittel genannt, oder einen oder mehrere Löslichkeitsvermittler.Formulations according to the invention can have one or more further ingredients (E), for example one or more anionic or zwitterionic surfactants, one or more enzymes, one or more enzyme stabilizers, one or more alkali carriers, one or more acids, 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, colorants, one or more fragrances, one or more thickeners, one or more organic solvents, one or more tabletting aids, one or more Disintegration agents, also called tablet disintegrants, or one or more solubilizers.

Beispiele für anionische Tenside sind C8-C20-Alkylsulfate, C8-C20-Alkylsulfonate und C8-C20-Alkylethersulfate mit einer bis 6 Ethylenoxideinheiten pro Molekül, beispielsweise solche der folgenden Formel:

        R12-O(CH2CH2O)u-SO3M

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 with one to 6 ethylene oxide units per molecule, for example those of the following formula:

R 12 -O (CH 2 CH 2 O) u -SO 3 M

R12 ist C8-C20-Alkyl, verzweigt oder vorzugsweise unverzweigt
Die Variable u ist im Bereich von 1 bis 6R 12 is C 8 -C 20 -alkyl, branched or preferably unbranched
The variable u is in the range from 1 to 6

Unter amphoteren Tensiden werden im Rahmen der vorliegenden Erfindung solche Substanzen bezeichnet, die unter Anwendungsbedingungen eine positive und eine negative Ladung aufweisen. Beispiele für bevorzugte amphotere Tenside, die auch als zwitterionische Tenside bezeichnet werden können, sind sogenannte Aminoxid-Tenside und Betaine oder auch Betain-Tenside. Viele Betaine weisen ein quaternisiertes Stickstoffatom und eine Carbonsäuregruppe pro Molekül auf. Besonders bevorzugtes Beispiel ist Cocoamidopropylbetain.In the context of the present invention, amphoteric surfactants are those substances which have a positive and a negative charge under application conditions. Examples of preferred amphoteric surfactants, also known as zwitterionic surfactants are so-called amine oxide surfactants and betaines or betaine surfactants. Many betaines have one quaternized nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example is cocoamidopropyl betaine.

Beispiele für Aminoxid-Tenside sind Verbindungen der allgemeinen Formel (VII)

        R13R14R15N→O     (VII)

wobei R13, R14 und R15 unabhängig voneinander aus aliphatischen oder cycloaliphatischen oder C2-C4-Alkylen oder C10-C20-alkylamido Gruppen gewählt wird. Besonders bevorzugt ist R13 gewählt aus C8-C20-Alkyl oder C2-C4-Alkylene C10-C20-alkylamido und R14 und R15 sind jeweils Methyl. Besonders bevorzugte Beispiele sind Lauryldimethalaminoxid und Cocoamidopropylaminoxid.Examples of amine oxide surfactants are compounds of the general formula (VII)

R 13 R 14 R 15 N → O (VII)

where R 13 , R 14 and R 15 are selected independently of one another from aliphatic or cycloaliphatic or C 2 -C 4 -alkylene or C 10 -C 20 -alkylamido groups. R 13 is particularly preferably selected from C 8 -C 20 -alkyl or C 2 -C 4 -alkylenes, C 10 -C 20 -alkylamido and R 14 and R 15 are each methyl. Particularly preferred examples are lauryl dimethalamine oxide and cocoamidopropylamine oxide.

In einer Ausführungsform der vorliegenden Erfindung kann erfindungsgemäße Formulierung im Bereich von 3 bis 50 Gew.-% anionisches oder zwitterionisches Tensid enthalten.In one embodiment of the present invention, the formulation according to the invention can contain in the range from 3 to 50% by weight of anionic or zwitterionic surfactant.

Erfindungsgemäße Formulierungen können ein oder mehrere Enzyme enthalten. Beispiele für Enzyme sind Lipasen, Hydrolasen, Amylasen, Proteasen, Cellulasen, Esterasen, Pectinasen, Lactasen und Peroxidasen.Formulations according to the invention can 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 can contain, for example, up to 5% by weight of enzyme, 0.1 to 3% by weight are preferred, in each case based on the total solids content of the formulation according to the invention.

Erfindungsgemäße Formulierungen können einen oder mehrere Enzymstabilisatoren enthalten. Enzymstabilisatoren dienen dem Schutz von Enzym - besonders während der Lagerung - gegen Schädigungen wie beispielsweise Inaktivierung, Denaturierung oder Zerfall etwa durch physikalische Einflüsse, Oxidation oder proteolytische Spaltung.Formulations according to the invention can contain one or more enzyme stabilizers. Enzyme stabilizers serve to protect enzymes - especially during storage - against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage.

Beispiele von Enzymstabilisatoren sind reversible Proteaseinhibitoren, beispielsweise Benzamidin-Hydrochlorid, Borax, Borsäuren, Boronsäuren oder deren Salze oder Ester, darunter vor allem Derivate mit aromatischen Gruppen, etwa ortho-, meta- oder para-substituierte Phenylboronsäuren, insbesondere 4-Formylphenyl-Boronsäure, beziehungsweise die Salze oder Ester der vorstehend genannten Verbindungen. Auch Peptidaldehyde, das heißt Oligopeptide mit reduziertem C-Terminus, insbesondere solche aus 2 bis 50 Monomeren, werden zu diesem Zweck eingesetzt. Zu den peptidischen reversiblen Proteaseinhibitoren gehören unter anderem Ovomucoid und Leupeptin. Auch spezifische, reversible Peptid-Inhibitoren für die Protease Subtilisin sowie Fusionsproteine aus Proteasen und spezifischen Peptid-Inhibitoren sind hierfür geeignet.Examples of enzyme stabilizers are reversible protease inhibitors, for example benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, including, in particular, derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, especially 4-formylphenylboronic acid, or the salts or esters of the aforementioned compounds. Peptide aldehydes, that is to say oligopeptides with a reduced C-terminus, in particular those made from 2 to 50 monomers, are also used for this purpose. The peptide reversible protease inhibitors include ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this.

Weitere Beispiele für Enzymstabilisatoren sind Aminoalkohole wie Mono-, Di-, Triethanol- und-Propanolamin und deren Mischungen, aliphatische Mono- und Dicarbonsäuren bis zu C12-Carbonsäuren, wie beispielsweise Bernsteinsäure. Auch endgruppenverschlossene Fettsäureamidalkoxylate sind geeignete Enzymstabilisatoren.Further examples of enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids up to C 12 -carboxylic acids, such as succinic acid. End-capped fatty acid amide alkoxylates are also suitable enzyme stabilizers.

Andere Beispiele für Enzymstabilisatoren sind Natrium-Sulfit, reduzierende Zucker und Kaliumsulfat. Ein weiteres Beispiel eines geeigneten Enzymstabilisators ist Sorbitol.Other examples of enzyme stabilizers are sodium sulfite, reducing sugars, and potassium sulfate. Another example of a suitable enzyme stabilizer is sorbitol.

Erfindungsgemäße Formulierungen können einen oder mehrere Builder (E), insbesondere Phosphat-freie Builder (E), enthalten. Im Rahmen der vorliegenden Erfindung zählt Verbindung (A) nicht als Builder (E). Beispiele für geeignete Builder (E) sind Silikate, insbesondere Natriumdisilikat und Natriummetasilikat, Zeolithe, Schichtsilikate, insbesondere solche der Formel α-Na2Si2O5, β-Na2Si2O5, und δ-Na2Si2O5, weiterhin Ethylendiamindibernsteinsäure und polymere Builder (E), beispielsweise Polycarboxylate und Polyasparaginsäure.Formulations according to the invention can contain one or more builders (E), in particular phosphate-free builders (E). In the context of the present invention, compound (A) does not count as builder (E). Examples of suitable builders (E) are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular 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 ethylenediamine disuccinic acid and polymeric builders (E), for example polycarboxylates and polyaspartic acid.

Ganz besonders bevorzugt enthalten erfindungsgemäße Formulierungen einen oder mehrere polymere Builder (E). Unter polymeren Buildern (E) werden dabei organische Polymere verstanden, insbesondere Polycarboxylate und Polyasparaginsäure. Polymere Builder (E) haben keine oder nur eine vernachlässigbare Wirkung als Tensid.Formulations according to the invention very particularly preferably contain one or more polymeric builders (E). Polymeric builders (E) are understood to mean organic polymers, in particular polycarboxylates and polyaspartic acid. Polymer builders (E) have no or only a negligible effect as a surfactant.

In einer Ausführungsform der vorliegenden Erfindung wählt man polymeren Builder (E) aus Polycarboxylaten, beispielsweise Alkalimetallsalze von (Meth)acrylsäurehomo- oder (Meth)acrylsäurecopolymeren.In one embodiment of the present invention, polymeric builders (E) are selected from polycarboxylates, 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 acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

In einer Ausführungsform der vorliegenden Erfindung wählt man polymeren Builder (E) aus einem oder mehreren Copolymeren, hergestellt aus mindestens einem Monomeren aus der Gruppe bestehend aus monoethylenisch ungesättigten C3-C10-Mono- oder Dicarbonsäuren oder deren Anhydriden, wie Maleinsäure, Maleinsäureanhydrid, Acrylsäure, Methacrylsäure, Fumarsäure, Itaconsäure und Citraconsäure sowie mindestens einem hydrophilen oder hydrophoben Comonomeren, wie nachfolgend aufgezählt.In one embodiment of the present invention, polymeric builders (E) are selected from one or more copolymers, prepared from at least one monomer from the group consisting of monoethylenically unsaturated C 3 -C 10 mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, Acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid and at least one hydrophilic or hydrophobic comonomer, 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.Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof such as, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C 22 -α-olefin, a mixture of C 20 -C 24 -α-olefins and polyisobutene with an average of 12 to 100 carbon atoms.

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-co-ethylenoxid)(meth)acrylat, Ethoxypolyethylenglykol(meth)acrylat, Ethoxypolypropylenglykol(meth)acrylat, Ethoxypolybutylenglykol(meth)acrylat und Ethoxypoly(propylenoxid-co-ethylenoxid)(meth)acrylat. Die Polyalkylenglykole enthalten dabei 3 bis 50, insbesondere 5 bis 40 und vor allem 10 bis 30 Alkylenoxideinheiten.Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups and nonionic monomers with a hydroxyl 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-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate) , Ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

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 vorstehend genannten Säuren, z. B. deren Natrium-, Kalium oder Ammoniumsalze.Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-meth-acrylamido-2- hydroxypropanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen-1-sulphonic acid, styrene-propene-1-sulphonic acid, 3-sulphate-2-sulpho-methacrylate, 3-sulphacrylate-2-sulpho-methacrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and salts of the aforementioned acids, e.g. B. their sodium, potassium or ammonium salts.

Besonders bevorzugte Phosphonatgruppen-haltige Monomere sind die Vinylphosphonsäure und ihre Salze.Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

Darüber hinaus können ein oder mehrere von Pfropfpolymer (B) verschiedene amphotere Polymere als polymere Builder (E) eingesetzt werden. Beispiele für amphotere Polymere sind Copolymere von mindestens einer ethylenisch ungesättigten Carbonsäure, gewählt aus Acrylsäure und Methacrylsäure, mindestens einem Amid, gewählt aus N-C1-C10-Alkyl(meth)acrylamid, Acrylamid und Methacrylamid, und mindestens einem Comonomer, gewählt aus DADMAC, MAP-TAC und APTAC.In addition, one or more amphoteric polymers other than graft polymer (B) can be used as polymeric builders (E). Examples of amphoteric polymers are copolymers of at least one ethylenically unsaturated carboxylic acid selected from acrylic acid and methacrylic acid, at least one amide selected from NC 1 -C 10 -alkyl (meth) acrylamide, acrylamide and methacrylamide, and at least one comonomer selected from DADMAC, MAP-TAC and APTAC.

Erfindungsgemäße Formulierungen können beispielsweise im Bereich von insgesamt 1 bis 75 Gew.-%, bevorzugt bis 50 Gew.-% Builder (E) enthalten, bezogen auf den Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.Formulations according to the invention can contain, for example, in the range from a total of 1 to 75% by weight, preferably up to 50% by weight, of builder (E), based on the solids content of the formulation according to the invention in question.

Erfindungsgemäße Formulierungen können beispielsweise im Bereich von insgesamt 1 bis15 Gew.-%, bevorzugt bis 10 Gew.-% polymeren Builder (E) enthalten, bezogen auf den Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.Formulations according to the invention can contain, for example, in the range from a total of 1 to 15% by weight, preferably up to 10% by weight, of polymeric builders (E), based on the solids content of the formulation according to the invention in question.

In einer besonders bevorzugten Ausführungsform enthält erfindungsgemäße Formulierung neben Pfropfpolymer (B) einen polymeren Builder (E). Das Gewichtsverhältnis polymerer Builder (E) zu Pfropfcopolymer (B) liegt dann vorzugsweise bei 30:1 bis 1:3, besonders bevorzugt bei 20:1 bis 1:1.In a particularly preferred embodiment, the formulation according to the invention comprises, in addition to graft polymer (B), a polymeric builder (E). The weight ratio of polymeric builder (E) to graft copolymer (B) is then preferably from 30: 1 to 1: 3, particularly preferably from 20: 1 to 1: 1.

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 can 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 cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetra-methylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferably used as aminoalkanephosphonates. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octasodium 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. Anstatt oder zusätzlich zu Alkaliträger können auch organische Amine, Alkanolamine wie z.B. Triethanolamin, oder Ammoniak eingesetzt werden.Formulations according to the invention can contain one or more alkali carriers. Alkali carriers, for example, ensure a pH value of at least 9 if an alkaline pH value is desired. For example, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates are suitable. The preferred alkali metal in each case is potassium, and sodium is particularly preferred. Instead of or in addition to alkali carriers, organic amines, alkanolamines such as e.g. Triethanolamine, or ammonia can be used.

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 Mangan-, Eisen-, Cobalt-, Ruthenium- oder Molybdäncarbonylkomplexe. 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 according to the invention can 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-salen complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

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 according to the invention can contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 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, weiterhin Polyethylenimin und Salze von Wismut oder Zink.Formulations according to the invention can contain one or more corrosion inhibitors. In the present case, these are to be understood as meaning those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol, furthermore polyethyleneimine and salts of bismuth or zinc.

In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße Formulierungen insgesamt im Bereich von 0,1 bis 1,5 Gew.-% Korrosionsinhibitor, bezogen auf den Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.In one embodiment of the present invention, formulations according to the invention contain a total of in the range from 0.1 to 1.5% by weight of corrosion inhibitor, based on the solids content of the formulation according to the invention in question.

Erfindungsgemäße Formulierungen können einen oder mehrere Gerüststoffe enthalten, beispielsweise Natriumsulfat.Formulations according to the invention can contain one or more builders, for example sodium sulfate.

Erfindungsgemäße Formulierungen können einen oder mehrere Entschäumer enthalten, gewählt beispielsweise aus Silikonölen und Paraffinölen.Formulations according to the invention can 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, bezogen auf den Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.In one embodiment of the present invention, formulations according to the invention contain a total of in the range from 0.05 to 0.5% by weight of defoamers, based on the solids content of the formulation according to the invention in question.

In einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen eine oder mehrere Säuren enthalten. Geeignet sind organische Säuren und anorganische Säuren. Als organische Säuren können beispielsweise Methansulfonsäure, Ameisensäure, Essigsäure, Glykolsäure, Milchsäure, Bernsteinsäure und/oder Adipinsäure gewählt werden. Als anorganische Säure wird vorzugsweise Salzsäure oder Phosphorsäure oder Amidosulfonsäure verwendet. Auch Mischungen von Säuren können eingesetzt werden, auch Mischungen aus organischen und anorganischen Säuren. Die Verwendung von Säuren in erfindungsgemäßen Formulierungen kommt insbesondere dann in Betracht, wenn der entsprechende Reiniger zusätzlich zu den erfindungsgemäßen Vorteilen auch noch über eine verbesserte Kalk-, Rost- oder Urinsteinentfernung verfügen soll, beispielsweise in Duschreinigern, Badreinigern oder WC Reinigern.In one embodiment of the present invention, formulations according to the invention can contain one or more acids. Organic acids and inorganic acids are suitable. As organic acids, for example methanesulfonic acid, formic acid, acetic acid, glycolic acid, lactic acid, succinic acid and / or adipic acid can be selected. The inorganic acid used is preferably hydrochloric acid or phosphoric acid or sulfamic acid. Mixtures of acids can also be used, including mixtures of organic and inorganic acids. The use of acids in formulations according to the invention comes into consideration in particular if the corresponding cleaner should also have improved lime, rust or urine scale removal in addition to the advantages according to the invention, for example in shower cleaners, bathroom cleaners or toilet cleaners.

In einer Ausführungsform enthalten feste erfindungsgemäße Formulierungen ein oder mehrere Disintegrationsmittel, auch Tablettensprengmittel genannt. Beispiele sind Stärke, Polysaccharide, beispielsweise Dextrane, weiterhin vernetztes Polyvinylpyrrolidon und Polyethylenglykolsorbitanfettsäureester.In one embodiment, solid formulations according to the invention contain one or more disintegrants, also called tablet disintegrants. Examples are starch, polysaccharides, for example dextrans, furthermore crosslinked polyvinylpyrrolidone and polyethylene glycol sorbitan fatty acid esters.

In einer Ausführungsform der vorliegenden Erfindung enthalten solche erfindungsgemäße Formulierungen, die bei Zimmertemperatur flüssig sind, einen oder mehrere Verdicker.In one embodiment of the present invention, such formulations according to the invention which are liquid at room temperature contain one or more thickeners.

Um die gewünschte Viskosität der betreffenden erfindungsgemäßen Formulierung zu erreichen, setzt man gelförmigen erfindungsgemäßen Formulierungen vorzugsweise ein oder mehrere Verdickungsmittel zu, wobei es sich als besonders vorteilhaft erweist, wenn die betreffende erfindungsgemäße Formulierung Verdickungsmittel im Bereich von 0,5 bis 30 Gew. -%, bevorzugt von 1 bis 20 Gew.-% und besonders bevorzugt von 2 bis 15 Gew. -% enthält, bezogen auf den Feststoffgehalt der betreffenden erfindungsgemäßen Formulierung.In order to achieve the desired viscosity of the formulation according to the invention in question, gel-like formulations according to the invention are preferably added one or more thickeners, it being particularly advantageous if the formulation according to the invention in question has thickeners in the range from 0.5 to 30% by weight, preferably from 1 to 20% by weight and particularly preferably from 2 to 15% by weight, based on the solids content of the formulation according to the invention in question.

Als Verdickungsmittel kann man aus der Natur stammende Polymere oder abgewandelte Naturstoffe oder synthetische Verdickungsmittel wählen.As a thickener, you can choose polymers derived from nature or modified natural substances or synthetic thickeners.

Als Beispiele für aus der Natur stammende Polymere, die als Verdickungsmittel im Rahmen der vorliegenden Erfindung geeignet sind, sind zu nennen: Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar-Mehl, Johannisbrotbaumkernmehl, Stärke, Dextrine, Xanthan, Gelatine und Casein.Examples of polymers derived from nature which are suitable as thickeners in the context of the present invention include: agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob gum, starch, dextrins , Xanthan, gelatin and casein.

Beispiele für Verdickungsmittel aus der Gruppe der abgewandelten Naturstoffe kann man beispielsweise aus der Gruppe der modifizierten Stärken und Cellulosen wählen. Beispielhaft seien Carboxymethylcellulose und andere Celluloseether, Hydroxyethylcellulose- und Hydroxypropy-lcellulose sowie Kernmehlether genannt.Examples of thickeners from the group of modified natural substances can be chosen, for example, from the group of modified starches and celluloses. Carboxymethyl cellulose and other cellulose ethers, hydroxyethyl cellulose and hydroxypropyl cellulose and gum ethers may be mentioned as examples.

Synthetische Verdickungsmittel sind gewählt aus teilweise vernetzten Poly(meth)acrylsäuren, hydrophob modifizierten Polyurethanen (HEUR Verdicker) und mit Fettalkoholethoxylaten veresterten Poly(meth)acrylsäure-Copolymeren (HASE Verdicker).Synthetic thickeners are selected from partially cross-linked poly (meth) acrylic acids, hydrophobically modified polyurethanes (HEUR thickeners) and poly (meth) acrylic acid copolymers esterified with fatty alcohol ethoxylates (HASE thickeners).

Ein besonders bevorzugt verwendetes Verdickungsmittel ist Xanthan.A particularly preferred thickening agent used is xanthan.

In einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen ein oder mehrere synthetische oder natürliche Wachse enthalten, besonders bevorzugt ist Carnaubawachs. Wachs wird speziell zur Ausrüstung empfindlicher Oberflächen zugesetzt, beispielsweise in Fußbodenreinigern.In one embodiment of the present invention, formulations according to the invention can contain one or more synthetic or natural waxes; carnauba wax is particularly preferred. Wax is specially added to finish sensitive surfaces, for example in floor cleaners.

In einer Ausführungsform der vorliegenden Erfindung können erfindungsgemäße Formulierungen ein oder mehrere organische Lösungsmittel enthalten. Beispielsweise kann man organische Lösungsmittel aus den Gruppen der Mono-Alkohole, Diole, Triole bzw. Polyole, der Ether, Ester und/oder Amide wählen. Besonders bevorzugt sind dabei organische Lösungsmittel, die wasserlöslich sind, wobei "wasserlösliche" Lösungsmittel im Sinne der vorliegenden Anmeldung Lösungsmittel sind, die bei Zimmertemperatur mit Wasser vollständig, d. h. ohne Mischungslücke, mischbar sind.In one embodiment of the present invention, formulations according to the invention can contain one or more organic solvents. For example, organic solvents can be chosen from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Organic solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.

Organische Lösungsmittel, die für erfindungsgemäße Formulierungen geeignet sind, wählt man vorzugsweise aus der Gruppe ein- oder mehrwertigen Alkohole, Alkanolamine oder Glykolether, die im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise wählt man organische Lösungsmittel aus Ethanol, n-Propanol, Isopropanol, Butanolen, Glykol, 1,2-Propandiol, oder Butandiol, Glycerin, Diglykol, Propyl- oder n-Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Di-ethylenglykolethylether, Propylenglykolmethyl-,-ethyl- oder -propylether, Dipropylenglykolmethyl-, oder -ethylether, Methoxy-, Ethoxy oder Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylenglykol-t-butylether sowie Mischungen von zwei oder mehr der vorstehend genannten organischen Lösungsmittel.Organic solvents which are suitable for formulations according to the invention are preferably chosen from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers which are miscible with water in the specified concentration range. Organic solvents are preferably chosen from ethanol, n-propanol, isopropanol, butanols, glycol, 1,2-propanediol, or butanediol, glycerol, diglycol, propyl or n-butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of two or more of the aforementioned organic solvents.

In einer speziellen Ausführungsform der vorliegenden Erfindung weisen erfindungsgemäße Formulierungen einen pH-Wert im Bereich von 1 bis 6 auf, bevorzugt 1 bis 4 Dabei wird im Falle von solchen erfindungsgemäßen Formulierungen, die bei Zimmertemperatur fest sind, der pH-Wert einer 1 Gew.-% wässrigen Lösung oder der flüssigen Phase einer 1 Gew.-% wässrigen Suspension bestimmt.In a special embodiment of the present invention, formulations according to the invention have a pH value in the range from 1 to 6, preferably 1 to 4. In the case of those formulations according to the invention which are solid at room temperature, the pH value is 1% by weight. % aqueous solution or the liquid phase of a 1 wt .-% aqueous suspension determined.

In einer weiteren speziellen Ausführungsform der vorliegenden Erfindung weisen erfindungsgemäße Formulierungen einen pH-Wert im Bereich von 6 bis 14 auf, bevorzugt 7 bis 10. Dabei wird im Falle von solchen erfindungsgemäßen Formulierungen, die bei Zimmertemperatur fest sind, der pH-Wert einer 1 Gew.-% wässrigen Lösung oder der flüssigen Phase einer 1 Gew.-% wässrigen Suspension bestimmt.In a further special embodiment of the present invention, formulations according to the invention have a pH value in the range from 6 to 14, preferably 7 to 10. In the case of such formulations according to the invention which are solid at room temperature, the pH value of 1 wt .-% aqueous solution or the liquid phase of a 1 wt .-% aqueous suspension determined.

Erfindungsgemäße Formulierungen eignen sich sehr gut als oder zur Herstellung von Klarspülmitteln für die Geschirrsreinigung, insbesondere für die maschinelle Geschirrreinigung (englisch "Automatic Dishwashing" oder kurz ADW). Erfindungsgemäße Formulierungen selbst und aus erfindungsgemäßen Formulierungen hergestellte Geschirrspülmittel - insbesondere aus erfindungsgemäßen Formulierungen hergestellte Phosphat-freie Geschirrspülmittel - weisen beim Geschirrspülen eine sehr gute Belagsinhibierung insbesondere auf Spülgut aus Glas auf. Insbesondere sind erfindungsgemäße Formulierungen auch gegen hartnäckige Flecken wirksam.Formulations according to the invention are very well suited as or for the production of rinse aids for dishwashing, in particular for automatic dishwashing (ADW for short). Formulations according to the invention themselves and dishwashing detergents produced from formulations according to the invention - in particular phosphate-free dishwashing detergents produced from formulations according to the invention - have very good deposit inhibition in dishwashing, in particular on items made of glass. In particular, formulations according to the invention are also effective against stubborn stains.

Beispiele für Spülgut aus Metall sind Bestecke, Töpfe, Pfannen und Knoblauchpressen, insbesondere Besteckteile wie Messer, Tortenheber und Vorlagebestecke.Examples of metal items to be washed are cutlery, pots, pans and garlic presses, in particular cutlery items such as knives, cake servers and cutlery.

Als Beispiele für Spülgut aus Glas seien dabei genannt: Gläser, gläserne Schüsseln, gläsernes Geschirr wie beispielsweise Glasteller, aber auch Gegenstände, die mindestens eine Oberfläche aus Glas aufweisen, das dekoriert oder nicht dekoriert sein kann, beispielsweise gläserne Vasen, durchsichtige Topfdeckel und Glasgefäße zum Kochen.Examples of items to be washed made of glass include: glasses, glass bowls, glass dishes such as glass plates, but also objects that have at least one surface made of glass that may or may not be decorated, for example glass vases, transparent pot lids and glass vessels Cook.

Als Beispiele für Spülgut aus Kunststoff seien dabei Teller, Tassen, Becher und Schüsseln aus Melamin, Polystyrol und Polyethylen genannt.Plates, cups, mugs and bowls made of melamine, polystyrene and polyethylene may be mentioned as examples of items to be washed made of plastic.

Als Beispiele für Spülgut aus Porzellan seien dabei Teller, Tassen, Becher und Schüsseln aus Porzellan, weiß oder farbig, jeweils mit oder ohne Dekoration, genannt.Examples of items to be washed made of porcelain are plates, cups, mugs and bowls made of porcelain, white or colored, each with or without decoration.

Erfindungsgemäße Formulierungen eignen sich nicht nur als oder zur Herstellung von Geschirrspülmitteln, sondern als oder zur Herstellung von Reinigungsmitteln für harte Oberflächen, beispielsweise Fußboden-Reiniger, Allzweck-Küchenreiniger oder Allzweck-Badezimmerreiniger.Formulations according to the invention are suitable not only as or for the production of dishwashing detergents, but as or for the production of cleaning compositions for hard surfaces, for example floor cleaners, all-purpose kitchen cleaners or all-purpose bathroom cleaners.

In Ausführungsformen, in denen man erfindungsgemäße Formulierungen beispielsweise als Allzweck-Badezimmerreiniger einsetzt, ist ein saurer pH-Wert bevorzugt, beispielsweise im Bereich von 1 bis 6.5. In Ausführungsformen, in denen man erfindungsgemäße Formulierungen als Allzweck-Küchenreiniger einsetzt, ist ein neutraler oder alkalischer pH-Wert bevorzugt, beispielsweise im Bereich von 7 bis 10.In embodiments in which formulations according to the invention are used, for example, as all-purpose bathroom cleaners, an acidic pH is preferred, for example in the range from 1 to 6.5. In embodiments in which formulations according to the invention are used as all-purpose kitchen cleaners, a neutral or alkaline pH is preferred, for example in the range from 7 to 10.

Um einen sauren pH-Wert zu erzielen, kann man Di- oder Polycarbonsäuren wie beispielsweise Essigsäure oder Weinsäure einsetzen.In order to achieve an acidic pH value, di- or polycarboxylic acids such as acetic acid or tartaric acid can be used.

Fußbodenreiniger und Allzweckreiniger sind für den Einsatz zur Reinigung empfindlicher Oberflächen bestimmt und haben in der Regel einen pH-Wert im Bereich von ca. 5 bis 8. In vielen Varianten sind Fußbodenreinigern und Allzweckreinigern zur Pflege der Oberflächen auch Pflegemittel wie Wachse zugesetzt. Das gleiche gilt für Handspülmittel und Lackreiniger, z. B. für Automobile.
Küchenreiniger weisen bevorzugt einen pH-Wert von 8 bis 14 auf und erreichen durch den stark alkalischen pH-Wert eine optimale Fettablösung bzw. Fettentfernung.Floor cleaners and all-purpose cleaners are intended for use in cleaning sensitive surfaces and usually have a pH value in the range of approx. 5 to 8. In many variants, floor cleaners and all-purpose cleaners also contain care products such as waxes for the care of the surfaces. The same applies to washing-up liquids and paint cleaners, e.g. B. for automobiles.
Kitchen cleaners preferably have a pH value of 8 to 14 and, thanks to the strongly alkaline pH value, achieve optimum fat removal or fat removal.

Bad-, Dusch- und WC-Reiniger weisen vorzugsweise einen sauren pH-Wert auf, beispielsweise von 1 bis 5, und erreichen durch den stark sauren pH-Wert eine optimale Kalk- bzw. Urinsteinablösung. Will man Bleichmittel in die Bad-, Dusch- oder WC-Reiniger hinzufügen, so sind Kombinationen von Chlorbleichmittel auf Basis von Hypochlorit mit Base bevorzugt. Eine andere bevorzugte Kombination sind Peroxid-Bleichmittel wie Wasserstoffperoxid mit Säuren. Derartige Kombinationen weisen eine bessere Lagerstabilität auf.Bath, shower and toilet cleaners preferably have an acidic pH value, for example from 1 to 5, and achieve optimal limescale or urine scale removal due to the strongly acidic pH value. If you want to add bleach to the bathroom, shower or toilet cleaners, combinations of chlorine bleach based on hypochlorite with base are preferred. Another preferred combination is peroxide bleaching agents such as hydrogen peroxide with acids. Such combinations have a better storage stability.

Harte Oberflächen sind im Rahmen der vorliegenden Erfindung Oberflächen von Materialien, die unter Reinigungsbedingungen nicht wasserlöslich und vorzugsweise auch nicht quellbar sind. Vorzugsweise haben sie eine Mohs-Härte von 3 oder mehr. Beispielhaft sind zu nennen: Fliesen, Glas, Glasfasern, Kacheln, Keramik, Porzellan, Emaille, Beton, Steinmaterialien, Leder, Metalle und Legierungen wie Eisen, Aluminium und Stahl, Hartholz, lackierte Oberflächen und Beschichtungen, Polymere und Kunststoffe wie beispielsweise Polyethylen, Polypropylen, PMMA, Polycarbonate, Polyester wie beispielsweise PET, Polystyrol und Hart-PVC, faserverstärkte Kunststoffe wie zum Beispiel Laminat, weiterhin Silizium-Oberflächen, beispielsweise von Wafern, sowie Verbundmaterialien. Harte Oberflächen können für das menschliche Auge glatt erscheinen oder aber eine Strukturierung aufweisen, zum Beispiel Erhebungen oder Vertiefungen aufweisen, zum Beispiel Furchen, und sie können konvex oder konkav sein.In the context of the present invention, hard surfaces are surfaces of materials which are not water-soluble and preferably also not swellable under cleaning conditions. Preferably they have a Mohs hardness of 3 or more. Examples include: tiles, glass, fiberglass, tiles, ceramics, porcelain, enamel, concrete, stone materials, leather, metals and alloys such as iron, aluminum and steel, hardwood, painted surfaces and coatings, polymers and plastics such as polyethylene, polypropylene , PMMA, polycarbonates, polyesters such as PET, polystyrene and rigid PVC, fiber-reinforced Plastics such as laminate, silicon surfaces, for example wafers, and composite materials. Hard surfaces can appear smooth to the human eye or they can have a structure, for example elevations or depressions, for example furrows, and they can be convex or concave.

Fliesen und Kacheln können beispielsweise zu Bädern, Küchen, Krankenhäusern oder auch zu Maschinen gehören.Tiles and tiles can, for example, belong to bathrooms, kitchens, hospitals or machines.

In einer Ausführungsform der vorliegenden Erfindung setzt man zum Reinigen Wasser mit einer Härte im Bereich von null bis 30 °dH, bevorzugt 2 bis 25 °dH ein, wobei unter deutscher Härte insbesondere die Summe aus Magnesium-Härte und Calcium-Härte zu verstehen ist.In one embodiment of the present invention, water with a hardness in the range from zero to 30 ° dH, preferably 2 to 25 ° dH, is used for cleaning, German hardness being understood in particular as the sum of magnesium hardness and calcium hardness.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen Formulierungen, im Rahmen der vorliegenden Erfindung auch erfindungsgemäßes Herstellverfahren genannt. Das erfindungsgemäße Herstellverfahren ist dadurch gekennzeichnet, dass man mindestens eine Verbindung (A), mindestens ein Pfropfcopolymer (B) und gegebenenfalls einen oder mehrere weitere Inhaltsstoffe (E) und gegebenenfalls Peroxid (D) bzw. Chlorbleichmittel (D) in einem oder mehreren Schritten miteinander vermischt gegebenenfalls in Anwesenheit von Wasser, und anschließend gegebenenfalls Wasser ganz oder partiell entfernt.The present invention also provides a process for the production of formulations according to the invention, also called production process according to the invention in the context of the present invention. The production process according to the invention is characterized in that at least one compound (A), at least one graft copolymer (B) and optionally one or more further ingredients (E) and optionally peroxide (D) or chlorine bleach (D) with one another in one or more steps mixed, if appropriate in the presence of water, and then if appropriate, water is completely or partially removed.

Verbindung (A), Pfropfcopolymer (B), Peroxid (D) und weitere Inhaltsstoffe (E) sind vorstehend beschrieben.Compound (A), graft copolymer (B), peroxide (D) and other ingredients (E) are described above.

In einer anderen Ausführungsform der vorliegenden Erfindung vermischt man Verbindung (A), einen oder mehrere weitere Inhaltsstoffe (E) und gegebenenfalls Peroxid (D) in trockener Form und gibt dann eine wässrige Lösung von Pfropfcopolymer (B) zu, entweder außerhalb oder innerhalb einer Spülmaschine.In another embodiment of the present invention, compound (A), one or more further ingredients (E) and optionally peroxide (D) are mixed in dry form and then an aqueous solution of graft copolymer (B) is added, either outside or inside a dishwasher .

In einer anderen Ausführungsform der vorliegenden Erfindung vermischt man Verbindung (A), Pfropfcopolymer (B) und einen oder mehrere weitere Inhaltsstoffe (E) und gegebenenfalls Peroxid (D) bzw. Chlorbleichmittel (D) in trockener Form und verpresst die so erhaltene Mischung zu Formköpern, insbesondere zu Tabletten.In another embodiment of the present invention, compound (A), graft copolymer (B) and one or more further ingredients (E) and optionally peroxide (D) or chlorine bleach (D) are mixed in dry form and the mixture thus obtained is compressed to form molded articles , especially about tablets.

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 Tensiden, einem oder mehreren Enzymen, einem oder mehreren Enzymstabilisatoren, einem oder mehreren Buildern (E), bevorzugt einem oder mehreren Phosphat-freien Buildern (E), insbesondere einem oder mehreren Polymeren Buildern (E), einem oder mehrere Cobuilder, einem oder mehreren Alkaliträgern, 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 the water is at least partially removed, it can be mixed with one or more further ingredients (E) for the formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more enzyme stabilizers, one or more several builders (E), preferably one or more phosphate-free builders (E), in particular one or more polymer builders (E), one or more cobuilders, one or more alkali carriers, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, with a 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 null bis 15 Gew.-%, bevorzugt 0,1 bis 10 Gew.-% aus erfindungsgemäßer Formulierung entfernt, indem man es verdampft, insbesondere durch Sprühtrocknung, Sprühgranulierung oder Kompaktierung.In one embodiment, the procedure is such that the water is completely or partially removed, for example down to a residual moisture content in the range from zero to 15% by weight, preferably 0.1 to 10% by weight, from the formulation according to the invention by removing it evaporated, 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, all or part of the water is removed at a pressure in the range from 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, all or part of the water is removed at temperatures in the range from 60 to 220.degree.

In einer anderen Ausführungsform entfernt man das Wasser nicht. Stattdessen kann man weiteres Wasser hinzufügen. Besonders bevorzugt gibt man außerdem ein Verdickungsmittel zu. Auf diesem Weg kann man erfindungsgemäße flüssige Formulierungen erhalten. Bei Zimmertemperatur können flüssige erfindungsgemäße Formulierungen beispielsweise in Gelform, als Emulsion oder als Lösung vorliegen.In another embodiment, the water is not removed. Instead, you can add more water. A thickener is also particularly preferably added. Liquid formulations according to the invention can be obtained in this way. At room temperature, liquid formulations according to the invention can be in gel form, as an emulsion or as a solution, for example.

Durch das erfindungsgemäße Herstellungsverfahren kann man erfindungsgemäße Formulierungen leicht erhalten.Formulations according to the invention can easily be obtained by the production process according to the invention.

Die erfindungsgemäßen Formulierungen können flüssig oder fest, ein- oder mehrphasig, als Tabletten oder in Form anderer Dosiereinheiten, beispielsweise als sogenannte Pouches, verpackt oder unverpackt bereitgestellt werden.The formulations according to the invention can be provided in liquid or solid form, in one or more phases, as tablets or in the form of other dosage units, for example as so-called pouches, packaged or unpacked.

Die Erfindung wird durch Arbeitsbeispiele weiter erläutert,The invention is further illustrated by working examples,

BeispieleExamples I. Herstellung von erfindungsgemäßen Klarspül-Formulierungen und von VergleichsformulierungenI. Production of rinse aid formulations according to the invention and of comparative formulations

Im Rahmen der vorliegenden Anmeldung sind Angaben in % Gewichtsprozent, wenn nicht ausdrücklich anders angegeben.In the context of the present application, data are in% by weight, unless expressly stated otherwise.

Pfropfcopolymer (B.1) entspricht Pfropfcopolymeren (B.4) aus WO 2015/197379 . Es wurde wie folgt hergestellt:
Eingesetzte Comonomere:

  • (a.1): Maltodextrin, kommerziell erhältlich als Cargill C*Dry MD01955
  • (b. 1): Acrylsäure
  • (c.1): [2-(Methacryloyloxy)ethyl]trimethylammoniumchlorid ("TMAEMC")
Graft copolymer (B.1) corresponds to graft copolymers (B.4) from WO 2015/197379 . It was made as follows:
Used comonomers:
  • (a.1): Maltodextrin, commercially available as Cargill C * Dry MD01955
  • (b.1): acrylic acid
  • (c.1): [2- (Methacryloyloxy) ethyl] trimethylammonium chloride ("TMAEMC")

Herstellung von Pfropfcopolymer (B.1)Production of graft copolymer (B.1)

In einem Rührreaktor wurden 220 g (a.1) in 618 g Wasser vorgelegt und unter Rühren auf 80°C erhitzt. Bei 80°C wurden simultan und über getrennte Zuläufe folgende Lösungen folgendermaßen zudosiert:

  1. a) eine wässrige Lösung aus 40,6 g (c.1) in 149 g Wasser, innerhalb von 4 Stunden.
  2. b) eine Lösung von 9,85 g Natriumperoxodisulfat in 68,0 g Wasser innerhalb von 5 h, gleichzeitig beginnend mit der Dosierung von a).
  3. c) eine Lösung aus 32,8 g (b.1) und 36,5 g Natronlauge (50%ig in Wasser), verdünnt mit 139 g Wasser, innerhalb von 2 Stunden, beginnend 2 Stunden nach Dosierungsbeginn von a).
220 g of (a.1) in 618 g of water were placed in a stirred reactor and heated to 80 ° C. with stirring. At 80 ° C., the following solutions were metered in simultaneously and via separate feeds:
  1. a) an aqueous solution of 40.6 g (c.1) in 149 g of water within 4 hours.
  2. b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water within 5 hours, starting at the same time with the metering of a).
  3. c) a solution of 32.8 g (b.1) and 36.5 g sodium hydroxide solution (50% in water), diluted with 139 g water, within 2 hours, beginning 2 hours after the start of dosing of a).

Nach vollständiger Zugabe der Lösungen a) bis c) wurde die Reaktionsmischung eine Stunde bei 80°C gerührt. Anschließend wurde eine Lösung von 0,73 g Natriumperoxodisulfat in 10,0 g Wasser zugegeben und weitere 2 Stunden bei 80°C gerührt. Anschließend kühlte man auf Zimmertemperatur ab und gab 8 g Biozid zu. Man erhielt eine 22,4 Gew.-% Lösung Pfropfcopolymer (B.1).After the complete addition of solutions a) to c), the reaction mixture was stirred at 80 ° C. for one hour. A solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was then added and the mixture was stirred at 80 ° C. for a further 2 hours. It was then cooled to room temperature and 8 g of biocide were added. A 22.4% by weight solution of graft copolymer (B.1) was obtained.

Als Biozid verwendete man eine 9 Gew.-% Lösung von 1,2-Benzisothiazolin-3-on in Wasser-Propylenglykol-Gemisch, kommerziell erhältlich als Proxel™ XL2 Antimicrobial. Mengenangaben in g sind tell qu'elle.The biocide used was a 9% by weight solution of 1,2-benzisothiazolin-3-one in a water / propylene glycol mixture, commercially available as Proxel ™ XL2 Antimicrobial. Quantities in g are tell qu'elle.

Es wurden erfindungsgemäße Formulierungen KSF.3 und Vergleichsformulierungen V-KSF.1 und V-KSF.2 hergestellt. Die Komponenten der Vergleichsformulierungen V-KSF.1 und V-KSF.2 und der erfindungsgemäßen Formulierung KSF.3 gehen aus Tabelle 1 hervor. Für die Herstellung wurde Wasser vorgelegt. Unter Rühren wurden dann Isopropanol, Anion-Tensid und nicht-ionisches Tensid und schließlich das Copolymer (B.1) zugegeben. Tabelle 1: Zusammensetzung von Vergleichsformulierungen V-KSF.1 und V-KSF.2 und von erfindungsgemäßer Formulierung KSF.3 V-KSF.1 V-KSF.2 KSF.3 Einsatzstoff Konz. Konzentration [g] Konzentration [g] Konzentration [g] Nio-Tensid 1 95% 5% 2,6 5% 2,6 5% 2,6 Anion-Tensid 1 40% 10% 12,5 10% 12,5 10% 12,5 Isopropanol 100% 5% 2,5 5% 2,5 5% 2,5 V-P.1 22% - - 1% 2,3 - - (B.1) 22,4% - - - - 1% 2,3 VE-Wasser 80% 32,4 79% 30,1 79% 30,1 Ansatzgröße [g] 50 50 50 Aussehen klar, farblos klar, leicht gelblich klar, farblos Konzentrationen sind stets in Gew.-% angegeben
Nio-Tensid 1: n-C16H33-O-(C2H4O)25-OH
Anion-Tensid 1: Natriumcumolsulfonat
Das Vergleichspolymer V-P.1 wurde gemäß Beispiel 4 aus EP 2 138 560 B1 hergestellt. Formulations KSF.3 according to the invention and comparative formulations V-KSF.1 and V-KSF.2 were produced. The components of the comparative formulations V-KSF.1 and V-KSF.2 and the formulation KSF.3 according to the invention are shown in Table 1. Water was provided for production. Isopropanol, anionic surfactant and non-ionic surfactant and finally the copolymer (B.1) were then added with stirring. Table 1: Composition of comparative formulations V-KSF.1 and V-KSF.2 and of formulation KSF.3 according to the invention V-KSF.1 V-KSF.2 KSF.3 Feedstock Conc. concentration [G] concentration [G] concentration [G] Nio surfactant 1 95% 5% 2.6 5% 2.6 5% 2.6 Anion surfactant 1 40% 10% 12.5 10% 12.5 10% 12.5 Isopropanol 100% 5% 2.5 5% 2.5 5% 2.5 VP.1 22% - - 1% 2.3 - - (B.1) 22.4% - - - - 1% 2.3 VE water 80% 32.4 79% 30.1 79% 30.1 Batch size [g] 50 50 50 Appearance clear, colorless clear, slightly yellowish clear, colorless Concentrations are always given in% by weight
Nio surfactant 1: nC 16 H 33 -O- (C 2 H 4 O) 25 -OH
Anion surfactant 1: sodium cumene sulfonate
The comparative polymer VP.1 was made according to Example 4 EP 2 138 560 B1 manufactured.

Versuche zur BelagsinhibierungAttempts to inhibit scale

Alle Spülversuche wurden in einer Geschirrspülmaschine der Fa. Miele, Typ G1222 SCL durchgeführt. Dabei wurde das Programm mit 65°C für den Waschzyklus und 65°C für den Klarspülzyklus gewählt. Die Prüfungen wurden mit aufgehärtetem Wasser mit einer Wasserhärte von 21 °dH (Ca/Mg):HCO3 (3:1):1.35 durchgeführt. Die eingebaute Wasserenthärtung (lonentauscher) wurde nicht mit Regeneriersalz regeneriert. Es wurden pro Spülversuch jeweils 18 g der Formulierung (siehe Tabelle Zusammensetzung der Formulierung für Belagsinhibierungstests) dosiert. Gleichzeitig mit der Formulierung wurden 50 g eines Ballastschmutzes zugegeben, bestehend aus Fett, Protein und Stärke.All washing tests were carried out in a Miele dishwasher, type G1222 SCL. The program with 65 ° C for the wash cycle and 65 ° C for the rinse cycle was selected. The tests were carried out with hardened water with a water hardness of 21 ° dH (Ca / Mg): HCO 3 (3: 1): 1.35. The built-in water softener (ion exchanger) was not regenerated with regeneration salt. In each rinsing test, 18 g of the formulation (see table Composition of the formulation for deposit inhibition tests) were dosed. At the same time as the formulation, 50 g of a ballast dirt were added, consisting of fat, protein and starch.

Im Programmschritt "Klarspülen" wurden jeweils 3 ml der jeweils angegebenen Klarspülformulierung (V-KS 1, V-KS 2 oder KS3) zudosiert.In the “final rinse” program step, 3 ml of the respective specified final rinse formulation (V-KS 1, V-KS 2 or KS3) were added.

Als Testspülgut dienen in jedem Reinigungsgang drei Edelstahl-Messer und drei Trinkgläser. Zwischen zwei Spülzyklen wurde jeweils eine Stunde gewartet, davon 10 min mit geschlossener Tür und 50 min mit geöffneter Tür der Geschirrspülmaschine.Three stainless steel knives and three drinking glasses serve as test items in each cleaning cycle. There was a waiting period of one hour between two washing cycles, 10 minutes of which with the door closed and 50 minutes with the dishwasher door open.

Nach Beendigung des 30. Spülganges wurde das Geschirr nach dem Trocknen aus der Maschine entfernt.After the 30th rinse cycle, the dishes were removed from the machine after drying.

Das Testspülgut wurde visuell in einer abgedunkelten Kammer unter Licht hinter einer Lochblende abgemustert und nach einer Notenskala von 1 (= starke Rückstände) bis 10 (= keine Rückstände) hinsichtlich Streifen und filmartiger Beläge beurteilt. Tabelle 2: Zusammensetzung der Formulierung für Belagsinhibierungstests Bestandteil [g] Racemisches MGDA-Na3, 78 Gew.-%, Rest ist Wasser 10 Zitronensäure als Trinatriumsalz Monohydrat 35 Polyacrylsäure Mw 4.000 g/mol als Natriumsalz, vollständig neutralisiert 5 Natriumpercarbonat, 2 Na2CO3·3 H2O2 10,2 Nicht-ionisches Tensid 1 4 Nicht-ionisches Tensid 2 1 Protease 2,5 Amylase 1 Na2Si2O5, kommerziell als Britesil® H 265 LC 2 TAED 4 Na2CO3 24,5 1-Hydroxyethan-1,1-diphosphonat Dinatriumsalz 0,8 Nicht-ionisches Tensid 1: n-C8H17-CH(OH)-CH2-O-(EO)22-CH(CH3)-CH2-O-n-C10H21
Nicht-ionisches Tensid 2: n-C10H21-CH(OH)-CH2-O-(EO)40-n-C10H21 Tabelle 3: Ergebnis des Belagsinhibierungstests mit Klarspüler Formulierung Klarspüler im Klarspülgang Filming Messer Filming Glas 18 g 3 ml V-KSF.1 4,3 4,0 18 g 3 ml V-KSF.2 5,5 4,0 18 g 3 ml KSF.3 5,7 5,7 The test items were visually sampled in a darkened chamber under light behind a perforated screen and assessed according to a rating scale from 1 (= strong residues) to 10 (= no residues) for stripes and film-like deposits. Table 2: Composition of the formulation for scale inhibition tests Component [g] Racemic MGDA-Na 3 , 78% by weight, the remainder is water 10 Citric acid as a trisodium salt monohydrate 35 Polyacrylic acid M w 4,000 g / mol as the sodium salt, completely neutralized 5 Sodium percarbonate, 2 Na 2 CO 3 • 3 H 2 O 2 10.2 Non-ionic surfactant 1 4th Non-ionic surfactant 2 1 Protease 2.5 Amylase 1 Na 2 Si 2 O 5 , commercially available as Britesil® H 265 LC 2 TAED 4th Na 2 CO 3 24.5 1-Hydroxyethane-1,1-diphosphonate disodium salt 0.8 Non-ionic surfactant 1: nC 8 H 17 -CH (OH) -CH 2 -O- (EO) 22 -CH (CH 3 ) -CH 2 -OnC 10 H 21
Non-ionic surfactant 2: nC 10 H 21 -CH (OH) -CH 2 -O- (EO) 40 -nC 10 H 21 formulation Rinse aid in the rinse cycle Filming knife Filming glass 18 g 3 ml V-KSF.1 4.3 4.0 18 g 3 ml V-KSF.2 5.5 4.0 18 g 3 ml KSF. 3 5.7 5.7

II. Herstellung von erfindungsgemäßen ReinigungsformulierungenII. Production of cleaning formulations according to the invention

Es wurden flüssige erfindungsgemäße Reinigungsformulierung RF.1 und flüssige Vergleichsformulierungen V-RF.2 und V-RF.3 hergestellt, indem man die Komponenten gemäß Tabelle 4 jeweils als wässrige Lösungen herstellte bzw. einsetzte und anschließend vermischte. Tabelle 4: Zusammensetzung Komponente Formulierung RF.1 V-RF.2 V-RF.3 (VI.1) 0,75 0,75 0,75 Nichtionisches Tensid 4 0,25 0,25 0,25 (B.1) 0,1 0 0 V-P.1 0 0,1 0 Wasser Add 100 pH-Wert 7,3 7,1 9,1 (VI.1): Alkylpolyglycosid-Mischung mit G1 = Glukose, y = 1,4, R10 = Wasserstoff, und R11 = n-C8-Alkyl/n-C10-Alkyl
Nichtionisches Tensid 4: 2-n-Propylheptanol, ethoxyliert mit 6 Äquivalenten Ethylenoxid Liquid cleaning formulation RF.1 according to the invention and liquid comparison formulations V-RF.2 and V-RF.3 were produced by producing or using the components according to Table 4 in each case as aqueous solutions and then mixing them. Table 4: Composition component formulation RF.1 V-RF.2 V-RF.3 (VI.1) 0.75 0.75 0.75 Nonionic surfactant 4 0.25 0.25 0.25 (B.1) 0.1 0 0 VP.1 0 0.1 0 water Add 100 PH value 7.3 7.1 9.1 (VI.1): Alkyl polyglycoside mixture with G 1 = glucose, y = 1.4, R 10 = hydrogen, and R 11 = nC 8 -alkyl / nC 10 -alkyl
Nonionic surfactant 4: 2-n-propylheptanol, ethoxylated with 6 equivalents of ethylene oxide

Um die primäre Reinigungsleistung zu bestimmen, wurde die IPP Form verwendet, wie sie in SÖFW, NO10/1986, Seite 371 veröffentlicht ist. Für den Test wurde eine künstliche IPP-Verschmutzung (83/21) folgender Zusammensetzung verwendet:
40 % Nytex 801 (Mineralöl), 36 % Benzin 80/110, 70 % Myritol 318 (Triglycerid) und 7 % Spezialschwarz 4. Dazu wurden das Mineralöl, Myritol und Benzin vermischt und das Spezialschwarz langsam eingerührt. Die so erhaltene Mischung wurde mit einem Ultraturraxgerät für 30 Minuten bei Geschwindigkeit 4 - 5 homogenisiert und danach 21 Tage lang in einem geschlossenen Erlenmeyer-Kolben auf einer Rührplatte gealtert. Anschließend wurde erneut für 30 Minuten homogenisiert.The IPP form, as published in SÖFW, NO10 / 1986, page 371, was used to determine the primary cleaning performance. An artificial IPP pollution (83/21) of the following composition was used for the test:
40% Nytex 801 (mineral oil), 36% petrol 80/110, 70% Myritol 318 (triglyceride) and 7% special black 4. For this, the mineral oil, myritol and petrol were mixed and the special black was slowly stirred in. The mixture obtained in this way was homogenized with an Ultraturrax device for 30 minutes at speed 4-5 and then aged for 21 days in a closed Erlenmeyer flask on a stir plate. It was then homogenized again for 30 minutes.

Je 0,16 ml dieser Verschmutzung wurden mit einer Bürste auf fünf Teststreifen aus PVC mit einer Fläche von 3, 5 -42 cm aufgetragen. Die verschmutzten Teststreifen wurden 90 Minuten lang getrocknet. Für die Reinigung wurden Schwämme vorbereitet, die bei 30°C in einer Waschmaschine gewaschen und anschließend in einem Trockner getrocknet. Vor Verwendung wurden die Schwämme mit deionisiertem Wasser angefeuchtet und durch einmaliges Auspressen des Wassers getrocknet. Die verschmutzten Teststreifen wurden in einem Gardner-Abrasionstester befestigt. Nach Auftrag von je 20 ml erfindungsgemäßer Reinigerformulierung bzw. Vergleichs-Reinigerlösung auf die vorbereiteten Schwämme reinigten diese die verschmutzten Teststreifen in 10 Abrasionszyklen mit einem Druck von 300 g. Die gereinigten Teststreifen wurden anschließend unter fließendem Wasser gespült und bei Raumtemperatur getrocknet.0.16 ml each of this contamination was applied with a brush to five test strips made of PVC with an area of 3.5-42 cm. The soiled test strips were dried for 90 minutes. Sponges were prepared for cleaning, washed in a washing machine at 30 ° C and then dried in a dryer. Before use, the sponges were moistened with deionized water and dried by squeezing out the water once. The soiled test strips were attached in a Gardner abrasion tester. After applying 20 ml of the inventive cleaning formulation or comparison cleaning solution to the prepared sponges, the sponges cleaned the soiled test strips in 10 abrasion cycles with a pressure of 300 g. The cleaned test strips were then rinsed under running water and dried at room temperature.

Nach 24 Stunden wurde die Reflektion der gereinigten Streifen gemessen. Die Ergebnisse sind in Tabelle 5 zusammengefasst. Tabelle 5: Ergebnisse der Reinigungsexperimente Formulierung Entfernung Verschmutzung in % F.1 70,6 V-F.2 67,1 V-F.3 63,5 After 24 hours, the reflection of the cleaned strips was measured. The results are summarized in Table 5. Table 5: Results of the cleaning experiments formulation Removal of soiling in% F.1 70.6 VF.2 67.1 VF.3 63.5

Claims (14)

  1. A formulation comprising
    (A) at least one nonionic surfactant,
    (B) at least one graft copolymer formed from
    (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains, obtainable by grafting of
    (b) at least one ethylenically unsaturated mono- or dicarboxylic acid and
    (c) at least one compound of the general formula (I)
    Figure imgb0014
     where the variables are defined as follows:
    R1 is selected from methyl and hydrogen,
    A1 is selected from C2-C4-alkylene,
    R2 are the same or different and are selected from C1-C4-alkyl,
    X- is selected from halide, mono-C1-C4-alkylsulfate and sulfate,
    (C) a total of zero to 0.5% by weight of methylglycinediacetic acid (MGDA) and glutaminediacetic acid (GLDA) and alkali metal salts of MGDA and GLDA and a total of zero to 0.5% by weight of citric acid or an alkali metal salt of citric acid, wherein figures in % by weight are based in each case on the solids content of the formulation in question.
  2. The formulation according to claim 1, wherein compound (c) is selected from ω-trimethylaminoethyl(meth)acrylatochloride.
  3. The formulation according to claim 1 or 2, wherein compound (A) is selected from alcohol alkoxylates and alkyl polyglycosides.
  4. The formulation according to any of claims 1 to 3, which comprises water.
  5. The formulation according to any of claims 1 to 4, which comprises at least one inorganic peroxide compound (D) or a chlorine bleach (D).
  6. The formulation according to any of claims 1 to 5, which comprises at least one acid or base.
  7. The formulation according to any of claims 1 to 6, which comprises:
    a total of in the range from 20% to 99% by weight of compound (A),
    a total of in the range from 1% to 40% by weight of graft copolymer (B),
    based in each case on the solids content of the formulation in question.
  8. The formulation according to any of claims 1 to 7, wherein the weight ratio of compound (A) to graft copolymer (B) is in the range from 1:2 to 20:1.
  9. The formulation according to any of claims 1 to 8, which is liquid at room temperature.
  10. The formulation according to any of claims 1 to 8, which is solid at room temperature.
  11. The use of formulations according to any of claims 1 to 10 for cleaning or rinsing of hard surfaces.
  12. The use according to claim 11 for cleaning or rinsing slabs, tiles, glass, stainless steel, wood, aluminum, enamel or ceramic.
  13. The use according to claim 11 or 12, wherein cleaning or rinsing is effected by hand or with the aid of a machine.
  14. A process for producing formulations according to any of claims 1 to 10, which comprises mixing at least one nonionic surfactant (A) and at least one graft copolymer (B) and optionally one or more further ingredients (E) and optionally peroxide (D) or chlorine bleach (D) with one another in one or more steps, optionally in the presence of water, and then optionally wholly or partially removing water.
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