EP3541911B1 - Formulations, leur fabrication et utilisation - Google Patents

Formulations, leur fabrication et utilisation 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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EP3541911A1 (fr
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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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Claims (14)

  1. Formulation, contenant
    (A) au moins un tensioactif non ionique,
    (B) au moins un copolymère greffé, construit à partir de
    (a) au moins une base de greffage, choisie parmi des monosaccharides, des disaccharides, des oligosaccharides et des polysaccharides non ioniques, et des chaînes latérales, pouvant être obtenues par greffage de
    (b) au moins un acide monocarboxylique ou dicarboxylique éthyléniquement insaturé et
    (c) au moins un composé de formule générale (I),
    Figure imgb0015
     les variables étant définies comme suit :
    R1 étant choisi parmi méthyle et hydrogène,
    A1 étant choisi parmi C2-4-alkylène,
    R2 étant identiques ou différents et choisis parmi C1-4-alkyle,
    X- étant choisi parmi halogénure, mono-C1-4-alkylsulfate et sulfate,
    (C) en tout de zéro à 0,5 % en poids d'acide méthylglycinediacétique (MGDA) et d'acide glutamique diacétique (GLDA) et de sels de métal alcalin de MGDA et de GLDA et en tout de zéro à 0,5 % en poids d'acide citrique ou d'un sel de métal alcalin d'acide citrique, les données en % poids se rapportant à chaque fois à la teneur en solides de la formulation concernée.
  2. Formulation selon la revendication 1, caractérisée en ce qu'on choisit le composé (c) parmi un chlorure de (méth)acrylate de ω-triméthylaminoéthyle.
  3. Formulation selon la revendication 1 ou 2, caractérisée en ce qu'on choisit le composé (A) parmi des alcoxylates d'alcools et des polyglycosides d'alkyle.
  4. Formulation selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle contient de l'eau.
  5. Formulation selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle contient au moins un composé inorganique de type peroxyde (D) ou un agent de blanchiment chloré (D) .
  6. Formulation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'elle contient au moins un acide ou une base.
  7. Formulation selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle contient :
    au total dans la plage de 20 à 99 % en poids de composé (A),
    au total dans la plage de 1 à 40 % en poids de copolymère greffé (B),
    à chaque fois par rapport à la teneur en solides de la formulation concernée.
  8. Formulation selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le rapport pondéral de composé (A) sur copolymère greffé (B) se situe dans la plage de 1:2 à 20:1.
  9. Formulation selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle est liquide à température ambiante.
  10. Formulation selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle est solide à température ambiante.
  11. Utilisation de formulations selon l'une quelconque des revendications 1 à 10 pour le nettoyage ou le rinçage de surfaces dures.
  12. Utilisation selon la revendication 11, caractérisée en ce qu'il s'agit du nettoyage ou du rinçage de carrelages, de carreaux, de verre, d'acier inoxydable, de bois, d'aluminium, d'émaux ou de céramique.
  13. Utilisation selon la revendication 11 ou 12, caractérisée en ce qu'on nettoie ou qu'on rince à la main ou à l'aide d'une machine.
  14. Procédé pour la préparation de formulations selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'on mélange ensemble au moins un tensioactif non ionique (A) et au moins un copolymère greffé (B) et éventuellement un ou plusieurs ingrédients supplémentaires (E) et éventuellement un peroxyde (D) ou un agent de blanchiment chloré (D) en une ou plusieurs étapes, éventuellement en présence d'eau, et ensuite on élimine éventuellement totalement ou partiellement l'eau.
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US10844326B2 (en) 2020-11-24
US20190367842A1 (en) 2019-12-05
ES2839948T3 (es) 2021-07-06
WO2018091326A1 (fr) 2018-05-24
EP3541911A1 (fr) 2019-09-25
PL3541911T3 (pl) 2021-03-22

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