WO2016102389A1 - Polymères pour nettoyant à effet de modification de surface - Google Patents

Polymères pour nettoyant à effet de modification de surface Download PDF

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Publication number
WO2016102389A1
WO2016102389A1 PCT/EP2015/080613 EP2015080613W WO2016102389A1 WO 2016102389 A1 WO2016102389 A1 WO 2016102389A1 EP 2015080613 W EP2015080613 W EP 2015080613W WO 2016102389 A1 WO2016102389 A1 WO 2016102389A1
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Prior art keywords
acids
cleaning agent
acid
group
aqueous composition
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PCT/EP2015/080613
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German (de)
English (en)
Inventor
Stefan Karsten
Marion Erbe
Martina Seiler
Doris Dahlmann
Michael Wolpers
Thomas Möller
Original Assignee
Henkel Ag & Co. Kgaa
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Priority to EP15816459.0A priority Critical patent/EP3237592A1/fr
Publication of WO2016102389A1 publication Critical patent/WO2016102389A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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 a hard surface cleaner, especially bathroom and kitchen ceramics containing surface modifying polymers based on organosilanes, and to the use of this hard surface cleaning detergent.
  • the object of the present invention was therefore to provide liquid detergents which, with consistently good or even improved cleaning performance, bring about an improvement in the dirt-repellent properties and in the water drainage on the surfaces cleaned with them.
  • organosilane-based polymeric compounds leads to a performance improvement of cleaning agents in the treatment of hard surfaces.
  • a first subject of the present invention is therefore a hard surface cleaner, in particular ceramic surfaces, containing, based on the total weight of the Cleaning agent, 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-%, of an acidic aqueous composition
  • an acidic aqueous composition comprising:
  • a surface cleaning agent according to the invention for cleaning and / or surface modification of hard surfaces, in particular of ceramic surfaces, for reducing limescale and improving the dirt-repellent properties of the surface.
  • Another aspect of the present invention is a method of cleaning hard surfaces using the detergents of the present invention.
  • an acidic aqueous composition comprising:
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.
  • At least one as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not to the absolute number of molecules. "At least one acid” thus means, for example, at least one type of acid, ie that one type of acid or a mixture of several different acids can be used. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • the International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymer ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • cleaning compositions or cleaning agents include, but are not limited to:
  • Means for cleaning and / or disinfecting hard surfaces such as all-purpose cleaners, floor cleaners, glass cleaners, kitchen cleaners, bath and sanitary cleaners, toilet cleaners, disinfectant cleaners.
  • Formulation types of cleansers include, but are not limited to: cleansing and disinfectant concentrates, liquid cleaners or disinfectants, sprays for cleansing or disinfecting, emulsions and gels.
  • a concentrate is usually an aqueous preparation with an increased active substance content, which is adjusted by dilution (usually with water) to the concentration corresponding to the respective application. Concentrates may preferably contain additional antioxidants or stabilizers.
  • the surfaces to be treated include, but are not limited to, glass, plastics, metals, steel, wood, stone materials, ceramics, cement, coatings, and composites, particularly ceramics.
  • the aqueous acidic composition is used in an amount of from 0.2 to 10% by weight, preferably from 0.2 to 5% by weight, based on the total weight of the cleaning agent.
  • concentrates of the cleaning composition according to the invention are present, they are diluted prior to use such that when applied to the surface the composition according to the invention is present in the abovementioned final concentration.
  • Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the agents according to the invention. These include, for example, in particular liquid, gel or pasty agents, packed both in large containers and in portions.
  • the agent can be applied to the surface.
  • the treatment of the surface is preferably carried out so that the agent is transferred to the surface by means of an absorbent fabric or that the agent is sprayed onto the surface.
  • the treatment can also be done, for example, by immersing the surface in the agent.
  • the agents of the present invention provide for easier soil removability and reduced tendency to re-soak and, in particular, improve the cleaning performance of hard surface cleaners. As a result, appropriately treated or cleaned surfaces are perceived longer than clean.
  • compositions according to the invention as additives for hard surface cleaners makes it possible, in a single work step, not only to clean a surface, but at the same time provide it with dirt-repellent properties. In this way, for example, a calcification is prevented. The treated surfaces remain clean longer and, moreover, the subsequent cleaning is greatly facilitated. This means that you need to clean the surfaces less often without sacrificing cleanliness and their subsequent cleaning is associated with less effort insofar as it can be done time-saving and / or milder detergents are needed.
  • an "organosilane” comprises a tetravalent silicon atom having four polar, covalently bonded substituents, at least one of these bonds being a covalent Si-C bond
  • a covalent Si-C bond always carries a nonhydrolyzable substituent
  • a hydrolyzable substituent is by definition not linked via such a covalent Si-C bond to the silicon atom of the organosilane compound.
  • organosilanes dissolved in water can undergo multiple hydrolysis and self-condensation reactions and are thus in an equilibrium between hydrolyzed and condensed form.
  • the acidic compositions used in hard surface cleaning compositions according to the invention comprise at least one oxoacid of phosphorus (i) and at least 0.2% by weight, calculated on the silicon element and the aqueous composition, of at least one organosilane compound (ii) having at least a hydrolyzable substituent and 1-3 non-hydrolyzable substituents, wherein at least one of the nonhydrolyzable substituents has at least one amino group, and wherein the absolute number of substituents on each silicon atom of an organosilane compound is 4.
  • the aqueous acidic composition according to the present invention may further contain other organosilane compounds which do not correspond to the organosilanes (ii).
  • the absolute amount of organosilanes, calculated on the silicon element, in the acidic aqueous compositions of the invention is not more than 15% by weight, based on the total weight of the composition.
  • the proportion of organosilanes (ii) in the total amount of organosilanes in the aqueous acid Composition calculated in each case based on the element silicon, is at least 30 mol%, preferably at least 40 mol%.
  • a hard surface cleaning agent in the sense of the present invention preferably contains organosilanes (ii) selected from the group consisting of compounds of the formula (1):
  • each X is a hydrolyzable substituent independently selected from the group consisting of alkoxy groups with not more than 4, preferably not more than 2 carbon atoms;
  • n and p are each independently an integer in the range of 1-4;
  • n is an integer in the range of 0-8, preferably in the range of 0-3;
  • y is an integer in the range of 1 to 3, preferably 1.
  • compounds of the formula (1) selected from the group consisting of monoaminoalkylalkoxysilanes, such as, for example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethyltrimethoxysilane,
  • Aminopropylmethyldimethoxysilane and aminopropylmethyldiethoxysilane Diaminoalkylalkoxysilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane; and so-called triaminoalkylalkoxysilanes, such as
  • Aminoethylaminoethylaminopropyltrimethoxysilane (trimethoxysilylpropyldiethylenetriamine) or aminoethylaminoethylaminopropyltriethoxysilane (triethoxysilylpropyldiethylenetriamine).
  • the cleaning agents according to the invention in addition to the organosilanes (ii) in the aqueous composition contain other, other organosilane compounds which are preferably selected from organosilane compounds having at least one hydrolyzable substituent and 1 to 3 non-hydrolyzable substituents, wherein at least one of non-hydrolyzable substituent carries a hydroxyl or oxirane (epoxy) group.
  • organosilane compounds which are selected from the group consisting of (3-glycidyloxypropyl) trimethoxysilane and / or (3-glycidyloxypropyl) triethoxysilane.
  • the proportion of such organosilanes having at least one hydroxyl or oxirane group, each calculated based on the element silicon, based on the total amount of organosilanes in the composition is at least 10 mol%, preferably at least 20 mol%.
  • Oxo acids of phosphorus (i) can be selected, for example, from the group consisting of: organophosphoric acids, phosphonic acids and / or phosphoric acids, the proportion of organophosphoric acids, based on the total amount of oxo acids of the phosphorus, being at least 10 mol%, preferably at least 40 mol%, particularly preferably at least 80 mol%, calculated based on the element phosphorus
  • the organophosphoric acids contained in the detergents according to the invention may, in various embodiments of the invention, have at least two phosphonic acid groups which are linked to one another via an alkylene, oxyalkylene or aminoalkylene group, where the alkylene, oxyalkylene or aminoalkylene groups may be substituted by amino, hydroxyl, , Aminoalkyl and / or hydroxyalkyl groups each having not more than 4 carbon atoms.
  • the shortest alkylene bridge linking two phosphonic acid groups preferably has not more than 4 carbon atoms. Examples of such organophosphoric acids are etidronic acid (1-hydroxyethylidenediphosphonic acid) and alendronic acid (4-amino-1-hydroxypropylsidene).
  • organophosphorus acids selected from the group of ⁇ -aminophosphonic acids of the formula (2) are particularly preferred:
  • n is an integer of at least 1 but not more than 5, preferably not more than 3; wherein m is an integer of at least 1 but not more than 5;
  • radicals X are independently selected from the group consisting of
  • the organophosphoric acids are selected from the group of ⁇ -aminophosphonic acids according to formula (3):
  • n is an integer of at least 1 but not more than 5, preferably not more than 3; wherein the radicals X are independently selected from the group consisting of hydrogen, aliphatic groups having not more than 4 carbon atoms, alkali metal cations, ammonium or quaternary ammonium cations;
  • the preferred ⁇ -aminophosphonic acids are nitrilotris (methylenephosphonic acid),
  • Ethylenediaminetetrakis methylenephosphonic acid
  • diethylenetriaminepentakis methylenephosphonic acid
  • their alkali metal, ammonium or quaternary ammonium salts methylenephosphonic acid
  • alkali metal, ammonium or quaternary ammonium salts methylenephosphonic acid
  • alkali metal, ammonium or quaternary ammonium salts methylenephosphonic acid
  • the acidic character of the aqueous composition is caused by the oxo acids of the phosphor.
  • the amount of acids having a pKA value for the first deprotonation step of more than 3.5 is therefore preferably less than 0.05% by weight, based on the total weight of the aqueous composition.
  • the acidic aqueous composition contains less than 0.05% by weight, in particular less than 0.01% by weight, of other acids.
  • formic acids and / or other, related carboxylic acids for example acetic acid, may additionally be used.
  • the pH of the aqueous acidic composition used according to the invention is in the range from 1 to 6, preferably in the range from 2.0 to 5.5.
  • the aqueous, acidic composition may be sol-gel systems.
  • the acidic, aqueous solutions of the above-described organosilanes are the starting materials, which then form sol particles by the hydrolysis and polycondensation of the organosilanes and then gel.
  • the resulting in the hydrolysis alcohols can be removed, for example, by vacuum distillation from the system.
  • compositions according to the invention may contain customary other constituents of cleaning agents, in particular cleaning agents for the treatment of hard surfaces, as far as they do not interact in an undesired manner with the substances used according to the invention.
  • other ingredients are, for example, surfactants, solvents, thickeners, other acids, salts, film formers, antimicrobial agents, builders, corrosion inhibitors, complexing agents, sequestering agents, electrolytes, foam inhibitors, Disintegrationstosstoffe, soil release agents or soil repellents, UV absorbers , Alkalis, preservatives, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers and fragrances and dyes.
  • the compositions should preferably contain not more than 30% by weight of other ingredients, preferably from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight, based on the total weight of the respective composition.
  • the other components contained in the cleaning agent according to the invention are to be selected according to their type and the amount used so that there are no undesired interactions with the organosilane compounds to be used according to the invention.
  • compositions according to the invention preferably comprise at least one surfactant which is selected from the anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.
  • surfactants which can be used according to the invention, reference is made in particular to International Publication WO2008 / 101909.
  • Suitable anionic surfactants are preferably Cs-ds-alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C8-C20-alkanesulfonates, Cs-ds-monoalkyl sulfates, Cs-ds-Alkylpolyglykolethersulfate with 2 to 6 ethylene oxide units (EO) in the ether part and Sulfosuccinic acid mono- and di-Cs-ds-alkyl esters.
  • Cs-ds-alkylbenzenesulfonates in particular having about 12 C atoms in the alkyl moiety
  • C8-C20-alkanesulfonates Cs-ds-monoalkyl sulfates
  • Cs-ds- ⁇ -olefinsulfonates sulfonated Cs-ds-fatty acids, in particular dodecylbenzenesulfonate, C8-C22-carboxylic acid amide ether sulfates, Cs-ds-alkylpolyglycol ether carboxylates, Cs-ds-N-acyltaurides, Cs-Ci8-N-sarcosinates and Cs -ds-Alkylisethionate or mixtures thereof are used.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic.
  • examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate.
  • Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable.
  • Particularly suitable nonionic surfactants are Cs-ds-alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), Cs-ds-carboxylic acid polyglycol esters with 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
  • Cs-ds-alcohol polyglycol ethers ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the
  • surfactants examples include oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units.
  • Particular preference is given to using Cs-ds-fatty alcohol polyglycol ethers having in particular 2 to 8 EO, for example C 12 -fatty alcohol + 7-EO-ethers, and Cs-to-alkylpolyglucosides having 1 to 2 glycoside units.
  • the nonionic surfactant is selected from the group comprising polyalkylene oxides, in particular alkoxylated primary alcohols, where the polyalkylene oxides may also be end-capped, alkoxylated fatty acid alkyl esters, amine oxides and alkyl polyglycosides and mixtures thereof.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R "') (R IV ) (R v ) N + CH 2 COO -, in which R" is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R IV and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-Alkylamidopropyldimethylcarboxymethylbetain.
  • Suitable cationic surfactants include u. the quaternary ammonium compounds of the formula (R VI ) (R V ") (R VI ") (R IX ) N + X " in which R VI to R IX are four identical or different, in particular two long and two short-chain, Alkyl radicals and X "are an anion, in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof.
  • the surfactant component comprises only one or more anionic surfactants, preferably Cs-Os-alkyl sulfates and / or Cs-Os-alkyl ether sulfates, and / or one or more nonionic surfactants, preferably Cs-ds fatty alcohol polyglycol ethers having 2 to 8 EO and / or Cs-Oo-alkylpolyglucosides having 1 to 2 glycoside units.
  • anionic surfactants preferably Cs-Os-alkyl sulfates and / or Cs-Os-alkyl ether sulfates
  • nonionic surfactants preferably Cs-ds fatty alcohol polyglycol ethers having 2 to 8 EO and / or Cs-Oo-alkylpolyglucosides having 1 to 2 glycoside units.
  • compositions according to the invention contain at least one nonionic surfactant which is (s) selected in particular from the ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and or propylene oxide units (PO) and the alkyl polyglycosides having 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
  • EO ethylene oxide
  • PO propylene oxide units
  • compositions according to the invention preferably contain surfactants in amounts of from 0.01 to 20% by weight, in particular from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.2 to 3% by weight. -%, in each case based on the total weight of the agent.
  • compositions according to the invention contain water or else additionally at least one nonaqueous solvent.
  • non-aqueous solvents are preferably those Solvents which are miscible in any proportions with water.
  • the nonaqueous solvents include, for example, monohydric or polyhydric alcohols, alkanolamines, glycol ethers and mixtures thereof.
  • the alcohols used are in particular ethanol, isopropanol and n-propanol.
  • ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration.
  • ether alcohols examples include ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred.
  • ethanol is used as the nonaqueous solvent.
  • Non-aqueous solvents may be present in the composition according to the invention in amounts of from 0.01 to 99.9% by weight, in particular from 0.1 to 50% by weight, and particularly preferably from 2 to 20% by weight, based in each case on Total weight of the agent.
  • Water is contained in the composition according to the invention generally in amounts of 1 to 98 wt .-%, in particular 50 to 95 wt .-%, and particularly preferably 80 to 93 wt .-%, each based on the total weight of the composition.
  • the cleaning agent according to the invention contains a thickener.
  • a thickener used in detergents and cleaning agents in the state of the art, such as organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, Gelatin, casein), organic modified natural products (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and the like, core flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners ( Polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas).
  • organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pect
  • polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers.
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci_4-alkanols formed esters (INCI acrylates copolymer), which include about the copolymers of methacrylic acid, Butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C-io-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with CW alkanols (INCI Acrylates / Oo-30 Alkyl Acrylate Crosspolymer).
  • Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or hydroxyethylmethylcellulose or cellulose acetate.
  • thickeners it is also possible to use phyllosilicates.
  • the agent according to the invention contains xanthan gum and succinoglycan gum.
  • agent according to the invention contains a thickener, it is generally present in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • the viscosity of the compositions according to the invention can be adjusted within a wide range depending on the intended use. Thus, for general purpose and bathroom cleaners, generally low, nearly water-thin formulations may be preferred, while for other uses, for example, toilet bowl cleaners, higher viscosity, thickened formulations may be preferred. In general, the viscosity of the inventive compositions in the range of 1 to 3000 mPas, preferably from 200 to 1500 mPas and particularly preferably from 400 to 900 mPas (Brookfield viscometer Rotovisco LV-DV II plus, spindle 31, 20 ° C, 20 U / min).
  • the agent according to the invention has a pH of less than 9, preferably a pH of from 1 to 6, particularly preferably from 2 to 5.5.
  • the cleaning agent according to the invention contains at least one acid.
  • Suitable acids are in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • acetic acid is not used as the acid.
  • the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof.
  • acids selected from the group comprising amidosulfonic acid, citric acid, lactic acid and formic acid are preferably used in amounts of 0.01 to 30 wt .-%, particularly preferably 0.2 to 15 wt .-%, each based on the total weight of the composition.
  • compositions according to the invention may contain film formers which may contribute to a better wetting of the surface.
  • the film former is selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably having a molecular weight between 200 and 20,000,000, more preferably between 5,000 and 200,000.
  • the film former is advantageously used in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • compositions according to the invention may furthermore contain one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1 wt.%, In particular of 0.05 to 0.5 wt.%, Particularly preferably of 0.1 to 0.3 wt .-%.
  • Suitable examples are antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine, iodophores and peroxides. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning agent.
  • Water-soluble and / or water-insoluble builders can be used in the compositions according to the invention.
  • Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces.
  • Typical builders which may be present in the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates.
  • Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders. With regard to further builders and / or cobuilders which can be used according to the invention and their preferred amounts used, reference is made to the publication WO2008 / 101909.
  • Suitable corrosion inhibitors are, for example, the following substances named according to INCI: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • further corrosion inhibitors which can be used according to the invention, in particular also glass
  • Chelants also called sequestering agents
  • the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents.
  • the complexing agents support the cleaning effect.
  • Suitable examples are the following according to INCI called complexing agents: aminotrimethylene, phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrates, diammonium EDTA, diethylenetriamines pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pen
  • alkalis it is also possible for alkalis to be present.
  • Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • the agents may further contain bleaching agents.
  • Suitable bleaching agents include peroxides, peracids and / or perborates, particularly preferred is hydrogen peroxide.
  • Sodium hypochlorite is less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline detergents.
  • a bleach activator may be included in addition to the bleaching agent.
  • the agent according to the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the composition in any form established in the art. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases.
  • an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage.
  • Suitable enzyme stabilizers are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • benzamidine hydrochloride borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic
  • stabilizers 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.
  • the agent according to the invention may finally contain one or more fragrances and / or one or more dyes.
  • dyes both water-soluble and oil-soluble dyes can be used, on the one hand the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the surfaces, especially against light ceramics, even with prolonged exposure should not be substantive.
  • suitable perfume is also limited only by possible interactions with the other detergent components.
  • a hard surface cleaner according to the invention may also contain one or more propellants (INCI propellants), usually in an amount of from 1 to 80% by weight, preferably from 1 to 5% by weight, in particular from 2 to 10% by weight, more preferably 2.5 to 8% by weight, most preferably 3 to 6% by weight.
  • ICI propellants usually in an amount of from 1 to 80% by weight, preferably from 1 to 5% by weight, in particular from 2 to 10% by weight, more preferably 2.5 to 8% by weight, most preferably 3 to 6% by weight.
  • blowing agents which can preferably be used according to the invention, reference is made to published patent application WO2008 / 101909.
  • a further subject of the present invention is also a product comprising a hard surface cleaner according to the invention and a spray dispenser.
  • the product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a transparent polyethylene or polyethylene terephthalate container.
  • Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference.
  • Trigger spray dispensers and pump atomizers have the advantage over compressed gas tanks that no propellant must be used.
  • suitable particles-passing attachments, nozzles, etc. so-called “nozzle valves”
  • enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.
  • This process can be carried out as a stand-alone treatment process for the surface, for example with dirt-repellent properties or one or more to provide the other properties which cause the agents according to the invention according to the teaching of the present invention.
  • the surface is brought into contact with a composition according to the invention.
  • the bringing into contact takes place at a temperature of 5 to 50 ° C, in particular 15 to 35 ° C.
  • the process according to the invention represents a purification process which serves to clean the surface.
  • the method according to the invention serves to treat a surface of ceramic, glass, stainless steel or plastic, very particularly preferably ceramic.
  • a further embodiment of the invention relates to the use of a composition according to the invention for protecting a hard surface against stains and / or for easier removal of new stains from the surface.
  • a further embodiment of the invention relates to the use of an agent according to the invention for water-repellent finishing of a hard surface and / or for shortening the drying time of a hard surface after exposure to water.
  • the treatment of a surface with the agents according to the invention hydrophobicizes this surface.
  • This facilitates the removal of dirt and at the same time causes water to bead off the surface and not wet it, thereby avoiding the formation of water droplets and thus the retention of residual stains.
  • This feature is particularly useful where surfaces are particularly prone to limescale, dirt and biofilm deposits, such as toilet bowls, sinks, bathtubs and shower stalls.
  • Another benefit of this feature is that water drains from treated surfaces faster, allowing them to dry faster.
  • a rinse with pure water is usually required after treating the surface with detergent. It is desirable that the surfaces dry quickly after this rinse, For example, because a fast-drying surface in a consumer enhances the impression of cleanliness.
  • the table below shows an example of a formulation used for the cleansing compositions according to the invention.
  • the new compound used is an acidic sol-gel product of phosphoric acid and three silanes. These are aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane and propyltrimethoxysilane.
  • the hydrolysis product methanol is removed from the system by vacuum distillation.
  • a black tile of the company Mosa (Mastricht, NL) (wall tile Royal Mosa code NEN.EN 1441 1 GL B III 15cmx15cm) is first cleaned with a commercially available scouring milk and then treated once with ethanol and cleaned.
  • the tile is "halved" with an adhesive strip, and a paper towel is used to apply a defined amount of the sol-gel compound of the invention as described in Example 1 (eg 0.5-1 ml) to one side of the tile distributed and then allowed to dry.
  • a defined amount of the sol-gel compound of the invention as described in Example 1 eg 0.5-1 ml

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne une composition de nettoyage, destinée à des surfaces dures, en particulier des surfaces en céramique dans les salles de bains et les cuisines, qui contient sur la base du poids total de la composition de nettoyage de 0,2 à 10% en poids d'une composition aqueuse acide comprenant : au moins un oxacide du phosphore et au moins 0,2% en poids, calculé sur la base de l'élément silicium et sur la base du poids total de la composition aqueuse acide, d'au moins un composé organosilane comportant au moins un substituant hydrolysable et de 1 à 3 substituants non hydrolysables. Au moins un des substituants non hydrolysables comporte au moins un groupe amino et le nombre total de substituants sur chaque atome de silicium d'un composé organosilane est de 4. L'invention concerne également l'utilisation de cette composition de nettoyage pour le nettoyage et/ou la modification de surfaces dures.
PCT/EP2015/080613 2014-12-23 2015-12-18 Polymères pour nettoyant à effet de modification de surface WO2016102389A1 (fr)

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DE102014226909.1 2014-12-23
DE102014226909.1A DE102014226909A1 (de) 2014-12-23 2014-12-23 Polymere für Reiniger mit Oberflächen-modifizierender Wirkung

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090081927A1 (en) * 2007-09-21 2009-03-26 Cabot Microelectronics Corporation Polishing composition and method utilizing abrasive particles treated with an aminosilane
US20100068396A1 (en) * 2008-05-23 2010-03-18 Jong Gi Kim Metal surface treatment solution and method of manufacturing steel sheet using the same
EP2557107A1 (fr) * 2011-08-12 2013-02-13 Evonik Goldschmidt GmbH Procédé de fabrication de polysiloxanes dotés de groupes contenant de l'azote
DE102013215440A1 (de) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Metallvorbehandlung mit sauren wasserhaltigen Zusammensetzungen umfassend Silane

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1002549A1 (fr) 1994-08-12 2000-05-24 The Procter & Gamble Company Composition destinée à lutter contre les mauvaises odeurs des surfaces inanimées
DE102007008655A1 (de) 2007-02-20 2008-08-21 Henkel Ag & Co. Kgaa Siderophor-Metall-Komplexe als Bleichkatalysatoren

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090081927A1 (en) * 2007-09-21 2009-03-26 Cabot Microelectronics Corporation Polishing composition and method utilizing abrasive particles treated with an aminosilane
US20100068396A1 (en) * 2008-05-23 2010-03-18 Jong Gi Kim Metal surface treatment solution and method of manufacturing steel sheet using the same
EP2557107A1 (fr) * 2011-08-12 2013-02-13 Evonik Goldschmidt GmbH Procédé de fabrication de polysiloxanes dotés de groupes contenant de l'azote
DE102013215440A1 (de) * 2013-08-06 2015-02-12 Henkel Ag & Co. Kgaa Metallvorbehandlung mit sauren wasserhaltigen Zusammensetzungen umfassend Silane

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DE102014226909A1 (de) 2016-06-23

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