EP3545066B1 - Copolymer enthaltende reinigungsmittelzusammensetzungen - Google Patents

Copolymer enthaltende reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP3545066B1
EP3545066B1 EP17807797.0A EP17807797A EP3545066B1 EP 3545066 B1 EP3545066 B1 EP 3545066B1 EP 17807797 A EP17807797 A EP 17807797A EP 3545066 B1 EP3545066 B1 EP 3545066B1
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structural units
mol
component
detergent composition
copolymers
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German (de)
English (en)
French (fr)
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EP3545066A1 (de
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Hannah Benson
Carsten Cohrs
Natascha SCHELERO
Mike SAHL
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Clariant International Ltd
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Clariant International Ltd
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the present invention relates to cleaning compositions containing one or more copolymers (polymer additives) which contain cationic (A) and macromonomeric (B) structural units and structural units (C), as well as one or more surfactants and water.
  • the invention further relates to the use of the cleaning compositions or the copolymers for treating hard surfaces, for example to achieve a cleaning effect on the surface, to impart hydrophilic properties to the surface, to create shine on the surface, to achieve permanent properties such as "anti-stain", “anti-trace” or “anti-streak” on the surface or to achieve a repair effect on the surface.
  • the invention further relates to a method for treating or cleaning a hard surface using the cleaning compositions or the copolymers.
  • Typical cleaning formulations allow the efficient cleaning of industrial, domestic or public hard surfaces. They generally consist of an aqueous solution of surfactants, in particular non-ionic and anionic surfactants, alcohol(s) to facilitate drying, bases to adjust the pH and, where appropriate, quaternary amines as disinfectants.
  • surfactants in particular non-ionic and anionic surfactants, alcohol(s) to facilitate drying, bases to adjust the pH and, where appropriate, quaternary amines as disinfectants.
  • WO 2013/170001 and WO 2013/170002 describe cleaning formulations containing alkoxylated polyethyleneimine polymers that improve the gloss on hard surfaces.
  • WO 2009/156067 describes cleaning formulations containing graft copolymers of saccharides that can be used to improve the gloss retention of hard surfaces and/or have hydrophilizing properties.
  • WO 2003/031546 describes aqueous antimicrobial cleaning compositions for the treatment of hard surfaces, with the result of maintaining or improving the gloss of the hard surfaces.
  • WO 98/49263 describes aqueous, acidic surface cleaners that contain a polymer additive and achieve an improved surface shine.
  • EP1196523B1 describes cleaning compositions intended for the treatment of hard surfaces in industry, the home or the general public and aimed in particular at imparting hydrophilic and protective properties to these surfaces.
  • US 2013/0303425 A1 describes cleaning agents for hard surfaces containing a polymer comprising modified and partially quaternized polyethyleneimines into which ethylene oxide units are incorporated.
  • EP 0 467 472 A2 discloses an aqueous composition for cleaning hard surfaces containing a cationic, quaternized polymer, preferably based on beta(trialkylammonium)ethyl methacrylate.
  • the object of the present invention was to develop polymer additives which are water-soluble or water-dispersible and can be added to cleaning agent compositions, and thus to provide cleaning agent compositions, in particular with the result that after their application to hard surfaces, advantageous gloss effects can be observed on the hard surfaces.
  • hard surface in the sense of the invention means a surface made of dimensionally stable materials, e.g. plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum and metal such as stainless steel, typically surfaces in the kitchen and sanitary area, for example in kitchens, bathrooms and toilets, in the home but also in the industrial area, for example in butcher shops, slaughterhouses, dairies, storage tanks for food or industrial products, as well as in the public area, such as building facades, in swimming pools or in train stations.
  • plastic plastic, ceramic, stone such as natural stone, porcelain, glass, wood, linoleum and metal such as stainless steel
  • WO 2012/076365 A1 discloses cationic copolymers containing cationic structural units and macromonomeric structural units and their use as additives for building material systems, in particular based on calcium sulfate.
  • WO 2008/049549 A2 describes hydrophobically modified cationic copolymers which have at least three different structural units and of which one structural unit has a terminal phenyl group or specially substituted phenyl group.
  • a significant improvement in water retention in aqueous building material systems based on hydraulic binders, such as cement, can be achieved even in the case of high salt loads.
  • Dispersions comprising inorganic particles, water and at least one water-soluble polymer are described.
  • the at least one water-soluble polymer has repeating units derived from monomers having at least one quaternary ammonium group, Repeating units derived from monomers having at least one carboxy group and repeating units derived from ester monomers containing polyalkoxyalkylene groups and having a number average molecular weight in the range from 3000 g/mol to 10,000 g/mol.
  • the dispersions can be used in particular for the production of concrete and can be processed over a very long period of time.
  • WO 2008/046652 A1 describes graft polymers obtainable by copolymerization of at least one specific macromonomer and at least one further monomer which has a polymerizable ethylenically unsaturated double bond and their use as dispersants, for example in pigment concentrates.
  • JP 2008-056711 A discloses copolymers having a number average molecular weight of 5,000 to 1,000,000 which contain structural units formed by polymerization of certain cationic monomers, polyoxyalkylene-modified monomers and crosslinkable monomers and which may additionally contain further structural units formed by polymerization of further monomers which can be copolymerized with the aforementioned monomers.
  • the copolymers can be used, for example, as antistatic agents for thermoplastic polymers.
  • An advantage of the invention is that the copolymers of component Z1) can be added to cleaning compositions, thereby producing a gloss effect on the hard surfaces to which they have been applied.
  • a further advantage of the invention is that the copolymers of component Z1) can be added to cleaning compositions and impart hydrophilic properties to the hard surfaces to which they have been applied.
  • the contact angle between a treated surface and a drop of water or a drop of an aqueous cleaning composition can be reduced.
  • the presence of traces or stains left on the hard surfaces by water or aqueous cleaning compositions that have come into contact with them is related to the phenomenon of contraction of the drops of water or drops of aqueous cleaning compositions when in contact with hard surfaces, which leave traces on the surfaces during subsequent drying.
  • the speed of drying of the surface can be improved.
  • the cleaning agent compositions according to the invention or the copolymers of component Z1) can be applied in such a way that they remain on the hard surface after application (“leave on” application) or are removed from it and preferably rinsed off with water (“rinse off” application).
  • the cleaning compositions according to the invention or the copolymers of component Z1) can be used advantageously, for example, on hard surfaces in bathrooms or kitchens, on floors or in toilets.
  • the one or more cationic structural units (A) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of [2-(acryloyloxy)ethyl]trimethylammonium chloride, [2-(acryloylamino)ethyl]trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium methosulfate, [2-(methacryloyloxy)ethyl]trimethylammonium chloride or methosulfate, [3-(acryloylamino)propyl]trimethylammonium chloride, [3-(methacryloylamino)propyl]trimethylammonium chloride and diallyldimethylammonium chloride (DADMAC), particularly preferably, the one or more cationic structural units (A) of the one or more copolymers of component Z1) of
  • the one or more macromonomer structural units (B) of the formula (III) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of polyethylene glycol vinyloxybutyl ether, polyethylene glycol-co-polypropylene glycol vinyloxybutyl ether (wherein I, on a molar average, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6), polyethylene glycol (meth)acrylate and polyethylene glycol-co-polypropylene glycol (meth)acrylate (wherein I, on a molar average, is a number from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 6).
  • (meth)acrylate encompasses both the corresponding acrylate compound and the corresponding methacrylate compound.
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of non-cationic acrylamides, non-cationic methacrylamides and N-vinyl-substituted lactams having 5 to 7 ring atoms.
  • the polymerization product selected from N-vinyl-substituted lactams having 5 to 7 ring atoms is preferred.
  • the groups SO 3 H, PO 3 H 2 , O-PO 3 H 2 and para-substituted C 6 H 4 -SO 3 H in the structural units of the formula (V) can also be present in salt form, preferably as NH 4 + -, alkali or alkaline earth salt and particularly preferably as NH 4 + - or as Na + -salt.
  • the structural units of the formula (V) preference is given to those which represent the polymerization product of at least one monomer species selected from the group consisting of [3-(acryloylamino)propyl]dimethylamine, [3-(methacryloylamino)propyl]dimethylamine, 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid, and particularly preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of 2-acryloylamino-2-methylpropanesulfonic acid and the salts of 2-acryloylamino-2-methylpropanesulfonic acid.
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning compositions according to the invention are selected from the structural units of the general formula (IV).
  • the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-methylolacrylamide, N-isopropylacrylamide and N-tertiary butylacrylamide and more preferably, the one or more structural units (C) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention represent the polymerization product of at least one monomer species selected from the group consisting of N,N-dimethylacrylamide and N-isopropylacrylamide.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain structural units (A), (B) and (C) as repeating structural units, but beyond that no further repeating structural units.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formula (VIII) in a particularly preferred embodiment of the invention.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formulas (IX) and/or (X) in a further particularly preferred embodiment of the invention.
  • the structural units of formula (X) can also be present in salt form, preferably as NH 4 + , alkali or alkaline earth salt and particularly preferably as NH 4 + or as Na + salt.
  • formulas (IX) and (X) preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of maleic anhydride, maleic acid and the salts of maleic acid.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formula (VII) in a further particularly preferred embodiment of the invention.
  • structural units of formula (VII) preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid, sodium methacrylate and potassium methacrylate.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain one or more structural units (D), these are selected from the structural units of the formulas (Va), (Vb) and/or (Vc) in a further particularly preferred embodiment of the invention.
  • the groups SO 3 H, PO 3 H 2 , O-PO 3 H 2 and para-substituted C 6 H 4 -SO 3 H in the structural units of the formula (Vb) can also be present in salt form, preferably as NH 4 + -, alkali or alkaline earth salt and particularly preferably as NH 4 + - or as Na + -salt.
  • Vc preferred are those which represent the polymerization product of at least one monomer species selected from the group consisting of vinyl butyl ether and vinyl acetate.
  • the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention contain structural units (A), (B), (C) and (D) as repeating structural units, but beyond that no further repeating structural units.
  • the structural units (A), (B), (C) and optionally (D) of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention are present in a random, block-shaped, alternating or gradient-like distribution in the copolymer.
  • the weight-average molecular weights M w of the one or more copolymers of component Z1) of the cleaning compositions according to the invention are from 10,000 to 250,000 g/mol, particularly preferably from 15,000 to 200,000 g/mol and especially preferably from 20,000 to 150,000 g/mol.
  • the radicals R s1 , R s2 , R s3 and R s4 are not defined in more detail here, but are only given for the sake of completeness as radicals bonded to the corresponding carbon atoms "C".
  • the structural units (A), (B) and (C) contained in the copolymers of component Z1) and the structural units (D) optionally additionally contained in the copolymers of component Z1) are examples of such repeating structural units.
  • Structural units which originate, for example, from radical initiators or from chain transfer regulators which may be used in the copolymerization do not represent recurring structural units. Accordingly, recurring structural units are not understood to mean, for example, terminal groups.
  • the amounts given for the structural units (A), (B), (C) and (D) in mol% are based on the total amount of repeating structural units contained in the respective copolymers of component Z1).
  • the copolymers of component Z1) of the cleaning agent compositions according to the invention can be prepared by methods familiar to the person skilled in the art.
  • the copolymers of component Z1) can particularly preferably be prepared by radical solvent polymerization.
  • Common solvents can preferably be polar solvents such as alcohols or water, as well as alcohol-water mixtures.
  • the polymerization is started by radical sources such as, for example, inorganic persulfates, organic azo compounds, peroxides, inorganic redox systems, or UV light.
  • chain transfer regulators can be used which form less reactive radicals in order to control the molecular weight of the copolymers.
  • Such chain transfer regulators are, for example, phenols, thiols, for example 2-mercaptoethanesulfonate sodium, or sodium hypophosphite.
  • the monomers for producing the copolymers of component Z1) and optionally a chain transfer regulator are dissolved in the solvent, oxygen is expelled, the temperature is then increased, and the radical initiator is added. The copolymerization is then carried out at the desired temperature for the desired period of time. The reaction mixture is then cooled if necessary and the copolymer formed is either further processed in solution or worked up, e.g. the solution containing the copolymer can be concentrated by partially evaporating the solvent or the solvent can be completely removed by evaporation or the copolymer can be isolated in another way, for example by freeze-drying or precipitation.
  • the cleaning compositions according to the invention contain the one or more copolymers of component Z1) in an amount of 0.005 to 10% by weight, preferably in an amount of 0.01 to 5% by weight and particularly preferably in an Amount of 0.1 to 0.5 wt.%, each based on the total weight of the cleaning composition.
  • the cleaning compositions according to the invention contain one or more surfactants as component Z2).
  • the one or more surfactants of component Z2) of the cleaning compositions according to the invention are selected from the group consisting of anionic, nonionic, amphoteric and cationic surfactants.
  • the cleaning compositions according to the invention can optionally contain anionic surfactants, e.g. alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and/or acylglutamates.
  • anionic surfactants e.g. alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, alkanesulfonates, alkyl ether carboxylic acids, sulfosuccinates, isethionates, taurates, glycinates and/or acylglutamates.
  • the alkyl chains of the surfactants mentioned can be synthetic or of natural origin and consist of 8 to 30, preferably 8 to 18 and particularly preferably 12 to 14 carbon atoms in a
  • Anionic surfactants used according to the invention are preferably aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfon
  • alkylbenzenesulfonates fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates as well as [alpha]-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • fatty alcohol sulfates and/or fatty alcohol ether sulfates are products of sulfation reactions on corresponding alcohols
  • Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • alkoxylated alcohols generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols.
  • alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols.
  • a complex mixture of addition products with different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
  • alkoxylation consists in the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
  • alkylbenzenesulfonate alkanesulfonate, alkyl ether sulfate or alkyl sulfate.
  • the anionic surfactants are usually used as salts, but also as acids.
  • the salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, especially preferably sodium salts.
  • surfactants can be nonionic, amphoteric and/or cationic surfactants, for example betaines, amidobetaines, amine oxides, amidoamine oxides, fatty alcohol polyglycol ethers, alkyl polyglycosides or quaternary ammonium compounds.
  • non-ionic surfactants can be, for example, alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers (fatty alcohol alkoxylates), alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also usable are Ethylene oxide-propylene oxide block copolymers and fatty acid alkanolamides and fatty acid polyglycol ethers.
  • Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glycosurfactants, such as alkyl polyglycosides, especially alkyl polyglucosides.
  • Suitable fatty alcohol polyglycol ethers are unbranched or branched, saturated or unsaturated C 8 -C 22 alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated C 10 -C 18 fatty alcohols having a degree of ethoxylation of less than 30, particularly preferably 1 to 20, especially preferably 1 to 12 and extremely preferably 1 to 8, for example C 12 -C 14 fatty alcohol ethoxylates with 8 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation.
  • Preferred alkyl polyglycosides are the alkyl polyglucosides, where the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - C 18 alkyl chains and the degree of oligomerization (DP) of the sugar is from 1 to 10, preferably from 1 to 6, particularly preferably from 1.1 to 3 and especially preferably from 1.1 to 1.7, for example C 8 -C 10 alkyl-1,5-glucoside (DP of 1.5).
  • the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - C 18 alkyl chains and the degree of oligomerization (DP) of the sugar is from 1 to 10, preferably from 1 to 6, particularly preferably from 1.1 to 3 and especially preferably from 1.1 to 1.7, for example C 8 -C 10 alkyl-1,5-glucoside (DP of 1.5).
  • amphoteric surfactants that can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids and biosurfactants.
  • Suitable betaines are the alkyl betaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI sultaines) and the amidosulfobetaines as well as the phosphobetaines.
  • betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl Betaine, Apricotamidopropylbetaine, Avocadamidopropylbetaine, Babassuamidopropylbetaine, Behenamidopropylbetaine, Behenylbetaine, Betaine, Canolamidopropylbetaine, Capryl/Capramidopropylbetaine, Carnitine, Cetylbetaine, Cocamidoethylbetaine, Cocamidopropylbetaine, Cocamidopropylhydroxysultaine, Cocobetaine, Cocohydroxysultaine, Coco/Oleamidopropylbetaine, Coco-Sultaine, Decylbetaine, Dihydroxyethyloleylglycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethylstearylglycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propy
  • the amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminopyrimidine Oxide, Dihydroxyethyl C 8 -C 10 Alkoxypropylamine Oxide, Dihydroxyethyl C 9 -C 11 Alkoxypropylamine Oxide, Dihydroxyethyl C 12 -C 15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxy
  • alkylamidoalkylamines are the following compounds named according to INCI: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate,
  • alkyl-substituted amino acids are the following compounds named according to INCI: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA-Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C 12 -C 15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA-Lauramino
  • the one or more surfactants of component Z2) of the cleaning compositions according to the invention are selected from the group consisting of fatty alcohol polyglycol ethers, alkyl polyglycosides, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates and quaternary ammonium compounds.
  • the proportion of the one or more surfactants of component Z2) in the cleaning agent composition according to the invention is preferably from 0.1 to 20% by weight and particularly preferably from 0.1 to 6.0% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.
  • the proportion of water in the cleaning agent compositions according to the invention is preferably from 10.00 to 99.8% by weight, particularly preferably from 40.00 to 98.00% by weight and especially preferably from 70 to 97.00% by weight, in each case based on the total weight of the cleaning agent compositions according to the invention.
  • the acids can be inorganic acids, e.g. hydrochloric acid, sulfuric acid, nitric acid, amidosulfonic acid and/or phosphoric acid.
  • the acids contained are organic acids, particularly preferably non-complexing acids such as lactic acid, formic acid, acetic acid, glycolic acid and/or gluconic acid.
  • Other preferred acids are malic acid, citric acid, tartaric acid, adipic acid and/or succinic acid.
  • the cleaning compositions according to the invention contain an acid.
  • the cleaning compositions according to the invention contain a mixture of two or more acids.
  • the amount of acid used is preferably from 0.1 to 10% by weight, particularly preferably from 0.2 to 5% by weight and especially preferably from 1 to 3% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.
  • a salt of an acid can also be added to buffer the pH value, in particular the sodium, potassium or magnesium salt, but also other alkali or alkaline earth salts or ammonium salts, in particular volatile amines such as monoethanolamine, ammonia, diethanolamines, but also triethanolamine.
  • the salt or salts of the acid or acids already present are used.
  • Suitable complexing agents are known to the person skilled in the art and are described by way of example in DE-A-10 2009 001 559 described.
  • Complexing agents are ingredients that can complex and inactivate metal ions in order to prevent their adverse effects on the stability or appearance of the agent, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with many ingredients. On the other hand, the complexing of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agent. In addition, the complexing agents support the cleaning effect.
  • Suitable examples are the following complexing agents designated according to INCI: Aminotrimethylene, Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentas
  • the proportion of component Z5) in the cleaning agent composition according to the invention is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3.0% by weight and especially preferably from 0.1 to 1.0% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.
  • Suitable water-soluble solvents are known to the person skilled in the art and are described by way of example in US2005/0239674 Alcohols, glycerin, glycols and glycol ethers are preferably used, preferably lower alcohols such as ethanol, isopropanol, butanol, isobutanol or alkylene glycols, e.g. propylene glycol, and glycol ethers, e.g. ethylene glycol n-butyl ether or propylene glycol n-butyl ether.
  • mixtures of several solvents are used.
  • the proportion of component Z6) in the cleaning agent composition according to the invention is preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 3% by weight and especially preferably from 0.5 to 1.5% by weight.
  • Suitable additives are other common ingredients of cleaning agents, for example disinfectants, pH adjusters, dyes, fragrances, buffers, viscosity regulators, corrosion inhibitors, organic and inorganic salts, optical brighteners, bleaches, antioxidants, opacifiers, hydrotropes, abrasives, preservatives, oxidizing agents and/or insecticides.
  • disinfectants pH adjusters, dyes, fragrances, buffers, viscosity regulators, corrosion inhibitors, organic and inorganic salts, optical brighteners, bleaches, antioxidants, opacifiers, hydrotropes, abrasives, preservatives, oxidizing agents and/or insecticides.
  • bleaching agents can be added to the composition.
  • Suitable bleaching agents include peroxides, peracids and/or perborates, H 2 O 2 is particularly preferred.
  • the cleaning agent compositions according to the invention can also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. They can be added to the cleaning agent compositions according to the invention in any form established according to the prior art. In the case of liquid or gel-like cleaning agent compositions according to the invention, these include in particular solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution.
  • capsules for example those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer that is impermeable to water, air and/or chemicals.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • Such granules for example by applying polymeric film formers, are advantageously low in dust and are stable in storage due to the coating.
  • enzyme stabilizers can be present in enzyme-containing cleaning agent compositions according to the invention in order to protect an enzyme contained in a cleaning agent composition according to the invention from damage such as, for example, inactivation, denaturation or decomposition due to physical influences, oxidation or proteolytic cleavage.
  • enzyme stabilizers are particularly suitable as enzyme stabilizers, depending on the enzyme used: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerin, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • Other suitable stabilizers are known from the prior art.
  • combinations of stabilizers are used, for example the combination of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other Dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • Preferred antimicrobial active ingredients are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group, as for example KH Wallotrousser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene” (5th edition - Stuttgart; New York: Thieme, 1995 ) describes.
  • disinfection, sanitation, antimicrobial effect and antimicrobial agent have the usual technical meaning within the scope of the invention, which is used, for example, by KH Wallophusser in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene” (5th edition - Stuttgart; New York: Thieme, 1995 ) is reproduced. While disinfection in the narrower sense of medical practice means the killing of - theoretically all - While sanitation means the elimination of all infectious germs as far as possible, including saprophytic germs that are normally harmless to humans.
  • thickeners are polysaccharides and heteropolysaccharides, in particular polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures.
  • polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • hydroxyethyl starch starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxyethylmethyl cellulose or cellulose acetate.
  • a particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 - 15 ⁇ 10 6 and is available, for example, from Kelco under the trade names Keltrol ® and Kelzan ® or from Rhodia under the trade name Rhodopol ® .
  • Layered silicates can also be used as thickeners. These include, for example, the magnesium or sodium-magnesium layered silicates from Solvay Alkali available under the trade name Laponite ® , in particular Laponite ® RD or Laponite ® RDS, as well as the magnesium silicates from Süd-Chemie, especially Optigel ® SH.
  • the amount of viscosity regulator if it is different from 0%, is preferably up to 0.5% by weight, particularly preferably from 0.001 to 0.3% by weight, especially preferably from 0.01 to 0.2% by weight and extremely preferably from 0.01 to 0.15% by weight, in each case based on the total weight of the cleaning agent composition according to the invention.
  • the viscosity of the cleaning agent composition according to the invention is preferably from 0.4 to 400 m•Pas.
  • cleaning compositions according to the invention can contain one or more corrosion inhibitors.
  • Suitable corrosion inhibitors are, for example, the following substances named according to INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate and Triisopropanolamine.
  • fragrance compounds can be used as fragrances, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohols and hydrocarbon type.
  • Fragrance compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • Ethers include, for example, benzyl ethyl ether
  • aldehydes include, for example, the linear alkanals with 8 to 18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, hydroxycitronellal, lilial and bourgeonal
  • ketones include, for example, benzyl ethyl ether.
  • Natural fragrance mixtures that are available from plant or animal sources can also be used as fragrances, e.g. pine, citrus, jasmine, lily, rose or ylang-ylang oil.
  • Essential oils with lower volatility, which are usually used as aroma components are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil.
  • the amount of fragrances in the cleaning compositions according to the invention is preferably from 0.001 to 2% by weight and particularly preferably from 0.01 to 2% by weight, based on the total weight of the cleaning compositions according to the invention.
  • the dyes and pigments optionally contained in the cleaning agent compositions according to the invention can be selected from the corresponding positive list of the Cosmetics Regulation or the EC list of cosmetic colorants.
  • Pearlescent pigments are also advantageously used, e.g. fish silver (guanine/hypoxanthine mixed crystals from fish scales) and mother of pearl (ground mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride (BiOCl), layer-substrate pigments, e.g.
  • mica/metal oxide silver-white pearlescent pigments made of TiO 2 , interference pigments (TiO 2 , different layer thicknesses), colored luster pigments (Fe 2 O 3 ) and combination pigments (TiO 2 /Fe 2 O 3 , TiO 2 /Cr 2 O 3 , TiO 2 /Prussian blue, TiO 2 /carmine).
  • the amount of dyes and pigments in the cleaning compositions according to the invention is preferably from 0.01 to 1.0% by weight, based on the total weight of the cleaning compositions according to the invention.
  • the proportion of component Z7) in the cleaning agent compositions according to the invention is preferably from 0.01 to 10% by weight, particularly preferably from 0.1 to 1% by weight and especially preferably from 0.1 to 0.5% by weight, in each case based on the total weight of the cleaning agent compositions according to the invention.
  • the cleaning agent compositions according to the invention or the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention are advantageously suitable for the treatment of hard surfaces, preferably made of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood.
  • the present invention therefore further relates to the use of a cleaning agent composition according to the invention or of at least one copolymer of component Z1) of the cleaning agent compositions according to the invention for the treatment of hard surfaces, preferably made of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood.
  • a cleaning agent composition according to the invention or of at least one copolymer of component Z1) of the cleaning agent compositions according to the invention for the treatment of hard surfaces, preferably made of ceramic, stone, porcelain, glass, stainless steel, metal, plastic, linoleum or wood.
  • the use according to the invention for the treatment of hard surfaces is carried out in order to achieve a cleaning effect on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to impart hydrophilic properties to the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to produce shine on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to improve the speed of drying of a hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention is preferably carried out for the treatment of hard surfaces in order to achieve permanent properties, preferably "anti-stain”, “anti-trace” or “anti-streak", on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to reduce the re-soiling of a hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to facilitate the renewed cleaning of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention is preferably carried out for the treatment of hard surfaces in order to achieve a repair effect of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention is preferably carried out for the treatment of hard surfaces in order to remove grease residues or lime soap residues on the hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied.
  • the use according to the invention is preferably carried out for the treatment of hard surfaces in order to remove lime on the hard surface to which the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention has been applied, or to reduce new lime deposits.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to minimize or prevent the formation of a biofilm on the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for the treatment of hard surfaces is preferably carried out in order to facilitate the rinsing of the hard surface to which the cleaning composition according to the invention or the at least one copolymer of component Z1) of the cleaning compositions according to the invention has been applied.
  • the use according to the invention for treating hard surfaces is carried out in such a way that the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention remain on the hard surface after application ("leave-on" application).
  • the use according to the invention for treating hard surfaces is carried out in such a way that the cleaning agent composition according to the invention or the at least one copolymer of component Z1) of the cleaning agent compositions according to the invention are removed from the hard surface after application and are preferably rinsed off with water ("rinse-off" application).
  • the use according to the invention for treating hard surfaces is carried out for cleaning hard surfaces in the bathroom, hard surfaces in the kitchen, floors or toilets.
  • the present invention also further relates to a method for treating or cleaning a hard surface, characterized in that the hard surface is brought into contact with a cleaning agent composition according to the invention or with at least one copolymer of component Z1) of the cleaning agent compositions according to the invention.
  • the preferred embodiments given above for the cleaning agent compositions according to the invention also apply in a corresponding manner to the inventive use of the cleaning agent compositions according to the invention or of the one or more copolymers of component Z1) of the cleaning agent compositions according to the invention for treating hard surfaces and for the inventive method for treating or cleaning a hard surface using a cleaning agent composition according to the invention or at least one copolymer of component Z1) of the cleaning agent compositions according to the invention.
  • AAPTAC [3-(Acryloylamino)-propyl]-trimethylammonium chloride (75 wt.% active in aqueous solution)
  • AMPS-Na-Salt 2-Acryloylamino-2-methylpropanesulfonic acid, Na salt 50 wt.% active in aqueous solution
  • DADMAC Diallyldimethylammonium chloride (65 wt.% active in aqueous solution)
  • DMAA N,N-Dimethylacrylamide (100% active)
  • MAPTAC [3-(Methacryloylamino)-propyl]-trimethylammonium chloride (50 wt.% active in aqueous solution)
  • MESNA 2-Mercaptoethanesulfonate sodium 100% active) Meth 1000 Polyethylene glycol-co-polypropylene glycol methacrylate, 1000 g/mol, 4-5 propylene glycol units (70 wt.% active in
  • the aqueous solution is then flushed with nitrogen for 30 minutes and heated to 60 °C if VA-44 is used as the initiator, or to 80 °C if Na 2 S 2 O 8 is used as the initiator.
  • the amount of initiator (VA-44 or Na 2 S 2 O 8 ) specified in Table 1 is dissolved in 10 g of distilled water and metered in over a period of 90 minutes. After dosing is complete, stirring is continued for a further hour at an internal temperature of 60 °C if VA-44 is used as the initiator, or at an internal temperature of 80 °C if Na 2 S 2 O 8 is used as the initiator.
  • the conversion of the reaction is checked by a subsequent analysis of the solid and any unreacted monomers are reacted by adding a small amount of a 10 wt. % aqueous solution of the previously used initiator until complete conversion is achieved.
  • the reaction mixture is then cooled to room temperature (20 - 23 °C).
  • Table 1 lists synthesis examples for copolymers of component Z1) of the cleaning compositions according to the invention.
  • Table 1 Substances used to prepare the copolymers Copolymer No. V-PEG 1100 V-PEG 5000 Meth 1000 Meth 5000 AAPTAC NIPAM DMAA DADMAC MAPTAC NVP AMPS-Na-Salt MS-Na-Salt Na-hypophosphite MESNA VA-44 Na2S2O8 dest.
  • Pillar PSS NOVEMA MAX Guard, 1x30 ⁇ & 2x1000 ⁇ 10 ⁇ m, 300 mm x 8 mm Detector: RI Oven temperature: 25°C Flow: 1 ml / minute Injection volume: 50 ⁇ l Eluent: 79.7 vol% 0.1M NaCl + 0.3 vol% TFA (trifluoroacetic acid) + 20.0 vol% ACN (acetonitrile) Calibration method: conventional calibration Standards: Poly(2-vinylpyridine) in the range of 1110 to 1 060 000 Dalton
  • Black, glossy ceramic tiles (10 ⁇ 10 cm) are pre-cleaned and then about 10 drops of the cleaning agent composition are applied to the center of the tiles.
  • the cleaning agent composition is evenly distributed on the tile using a folded cellulose kitchen towel. After the tiles have dried vertically for at least 30 minutes, a visual assessment (grade 1 - 10) of the tiles is carried out, with 1 being considered the best and 10 the worst grade.
  • Example formulations with and without copolymer of component Z1) of the cleaning compositions according to the invention were prepared and Gloss tests were conducted with these formulations.
  • the example formulations and gloss results are shown in Table 2.
  • Table 2 Example formulations and gloss results
  • Cleaning agent compositions were prepared analogously using copolymers 7 and 10-20.
  • Table 3 shows that by using the copolymers of component Z1) of the cleaning agent compositions according to the invention in commercial cleaners, better shine results can be achieved compared to the corresponding commercial cleaners without the addition of a copolymer of component Z1).
  • the tests were carried out using the quartz crystal microbalance QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring, Q-Sense, Västra Frölinda, Sweden).
  • the method is based on the change in the natural frequency of a piezoelectric quartz crystal as soon as it is loaded with a mass.
  • the surface of the quartz can be modified by spin coating or vapor deposition.
  • the quartz oscillator is located in a measuring cell.
  • the measuring cell is a flow cell into which the solution to be examined is pumped from storage vessels.
  • the pump speed is kept constant during the measurement. Typical pump speeds are between 50-250 ⁇ l/minute. During a measurement, it is important to ensure that the tubes and measuring cell are free of air bubbles.
  • Each measurement begins with the recording of the baseline, with respect to which all frequency and dissipation measurements are set as the zero point.
  • quartz crystals with a 50 nm thick silicon dioxide coating QSX303, Q-Sense, Västra Frölinda, Sweden
  • quartz crystals with a 50 nm thick stainless steel (SS2343) coating QSX304 Q-Sense, Västra Frölinda, Sweden
  • Aqueous solutions of the copolymers of component Z1) of the cleaning compositions according to the invention with an active content of 2000 ppm were investigated. Tap water with 20° dH was used as the water. The pH was adjusted to pH 10 with NaOH or citric acid.
  • Table 4 Adsorption of copolymers on silica: Copolymer No. Adsorbed mass [ng/cm 2 ] 5 264.4 3 275.9 6 355.8 4 142.5 7 348.0 19 102.7 20 330.4 Copolymer No. Adsorbed mass [ng/cm 2 ] 5 129.7 3 153.6 19 121.0 20 156.6
  • the contact angles were measured on various surfaces (ceramic, glass, stainless steel) by modifying the surfaces using the following method: The surfaces were dipped three times for 2 minutes in fresh demineralized water (deionized water) and then dipped in the respective aqueous copolymer solution for 20 minutes at room temperature while stirring to modify them. The surfaces were then dried with a gentle stream of nitrogen. The contact angle was measured on the surfaces prepared in this way using deionized water (apparatus: drop analyzer from Krüss, Hamburg, model DSA 100).
  • the height of the contact angle of a water drop on a surface is a measure of its hydrophilization.
  • a very hydrophilic surface is completely wetted by a water drop. This phenomenon is also called spreading of the drop.
  • Copolymers of component Z1) of the cleaning compositions according to the invention were investigated as an aqueous solution with an active content of 2000 ppm. Tap water with 20° dH was used as the water. The pH value was adjusted to pH 10 with NaOH or citric acid. Table 6 Contact angle on black ceramic tile Copolymer No. Contact angle of water Untreated 18° 5 8° 3 Drop spreads 6 4.2° 4 15° 7 5° 19 Drop spreads 20 Drop spreads Copolymer No. Contact angle of water Untreated 39° 6 Drop spreads 4 Drop spreads 7 Drop spreads Copolymer No. Contact angle of water untreated 15° 5 Drop spreads 3 Drop spreads 19 8° 20 13°
  • the topography of the surface of a damaged black tile was determined before and after treatment with aqueous solutions of the copolymers of component Z1) of the cleaning agent compositions according to the invention with an active content of 2000 ppm (equipment: contact-free optical 3D surface characterization from Sensofar, Barcelona, Model S neox).
  • equipment contact-free optical 3D surface characterization from Sensofar, Barcelona, Model S neox.
  • various 3D parameters can be calculated by segmenting the topography of a surface into surface elements. These parameters provide information on height information (calculation according to ISO 25178) and roughness (calculation according to ISO 4287).
  • Table 9 Roughness of a black damaged tile before and after copolymer treatment Copolymer No. Roughness untreated [nm] Roughness after treatment [nm] 3 71* 36* 6 140 94.6 4 110 108 7 86 85 * Changing the roughness of a black tile

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JP7211730B2 (ja) * 2018-08-09 2023-01-24 花王株式会社 バイオフィルム形成抑制剤及びバイオフィルム形成抑制方法
EP3771339A1 (en) * 2019-07-29 2021-02-03 The Procter & Gamble Company Disinfectant composition
EP3771742A1 (de) * 2019-07-30 2021-02-03 Henkel AG & Co. KGaA Toilettenstein mit verbessertem glanz
CA3148977A1 (en) 2019-09-26 2021-04-01 Ecolab Usa Inc. High alkaline solvent-based degreaser and cleaner with diutan gum as a primary thickening system
EP3868854A1 (en) * 2020-02-20 2021-08-25 Clariant International Ltd Cleaning compositions comprising copolymers and their use
WO2022209884A1 (ja) * 2021-03-30 2022-10-06 花王株式会社 菌付着抑制剤及び菌付着抑制方法

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DE102016223590A1 (de) 2018-05-30
AR110256A1 (es) 2019-03-13
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US20200080029A1 (en) 2020-03-12
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