WO2005017083A1 - Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides - Google Patents

Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides Download PDF

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Publication number
WO2005017083A1
WO2005017083A1 PCT/EP2004/008863 EP2004008863W WO2005017083A1 WO 2005017083 A1 WO2005017083 A1 WO 2005017083A1 EP 2004008863 W EP2004008863 W EP 2004008863W WO 2005017083 A1 WO2005017083 A1 WO 2005017083A1
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WIPO (PCT)
Prior art keywords
acid
cleaning agent
cleaning
agent according
carbonate
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PCT/EP2004/008863
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German (de)
English (en)
Inventor
Johannes Zipfel
Andreas Buhl
Brigitte Giesen
Michael Dreja
Christian Kropf
Wolfgang Von Rybinski
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from DE10337805A external-priority patent/DE10337805A1/de
Priority claimed from DE10348153A external-priority patent/DE10348153A1/de
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2005017083A1 publication Critical patent/WO2005017083A1/fr

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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/24—Mineral surfaces, e.g. stones, frescoes, plasters, walls or concretes

Definitions

  • the present invention relates to a cleaner for the gentle treatment of carbonate-containing acid-sensitive surfaces.
  • the surface cleaning agents normally used are generally not suitable for cleaning carbonate-containing acid-sensitive surfaces such as marble without damaging them. This is due to the fact that the agents for carrying out effective cleaning generally have an acidic pH value, but this naturally leads to damage to the acid-sensitive surface.
  • Marble for example, consists of calcium carbonate in the form of calcite or a mixture of calcium and magnesium carbonate. Due to the relatively high solubility of these carbonates, they are converted into the soluble form using weak acids.
  • EP0748864 and EP0780465 describe cleaning agents with a pH value between 6 and 9. It is explicitly pointed out that a pH value below 6 is not suitable, since this would damage the marble. Although these neutral or slightly basic cleaning agents do not damage the marble, the cleaning effect achieved is generally not satisfactory, especially with regard to the removal of stubborn dirt and limescale stains.
  • Multi-stage, complex processes are also described in the prior art, with which the marble surface is to be rendered permanently inert to acids.
  • No. 4,738,876 describes a process in which the stone surface is first treated with a solution with a pH between 0.1 and 2, the solution containing, in addition to the acid and water, a detergent, an organic solvent and tin chloride. After the surface has dried, a crystallizing agent is then applied to the surface. In a special embodiment, this can be zinc hexafluorosilicate.
  • US 5,780,111 describes a method for rendering the surface inert, in which the stone surface is first treated with a solution comprising zinc sulfate, an abrasive, a thickener and a wetting agent. After removing this mixture using polishing agent and water, the surface is treated with a solution comprising alkaline earth metal and zinc fluorosilicates, an aliphatic monocarboxylic acid and a wetting agent. This step is followed by a few more treatment steps.
  • DE257446 describes a process for cleaning marble, in which the marble is coated with a mixture of water glass, kaolin and zinc oxide. The coating produced in this way flakes off again automatically after drying.
  • Dishwashing detergents which contain polyvalent cations, and in particular zinc salts, are also described. The purpose is to prevent the corrosion of glassware by adding the multivalent cations.
  • the object of the present invention was to provide a cleaning agent which enables effective cleaning of acid-sensitive carbonate-containing surfaces in a simple and gentle manner.
  • the present invention therefore relates to a cleaning agent which has a pH between 2 and 6, in particular between 3 and 5, and contains divalent metal ions, the divalent metal ions being those which form sparingly soluble salts with carbonate.
  • the present invention relates in particular to the use of such a cleaning agent for cleaning surfaces, in particular hard surfaces and / or stone surfaces and / or acid-sensitive surfaces, preferably acid-sensitive carbonate-containing surfaces, especially marble surfaces.
  • the present invention therefore also relates to a process for cleaning surfaces, in particular hard surfaces and / or stone surfaces and / or acid-sensitive surfaces, preferably acid-sensitive carbonate-containing surfaces, especially marble surfaces, characterized in that the surface is coated with a cleaning agent according to the invention is treated.
  • the cleaning agent can in particular be a household cleaner, a cleaner for industrial plants or an institutional cleaner.
  • the cleaner is one for cleaning hard surfaces, such as floors, tiles, tiles, sinks, bathtubs and other hard surfaces in the household, in industrial plants, in public sanitary facilities, public buildings, Hospitals, hotels, schools, swimming pools, bathing establishments, saunas, sports facilities or in medical or massage practices.
  • the cleaning agent can in particular also be a sterilizing or disinfecting agent which can contain further components as are known to the person skilled in the art for such a agent.
  • the pH of the cleaning agent according to the invention is therefore preferably in a range between 2 and 6, particularly preferably between 3.5 and 5.5, especially between 3.8 and 4.5.
  • Any acid and base known to the person skilled in the art can be used to set the desired pH.
  • the appropriate pH adjusting agent is known to the person skilled in the art. Alkali metal hydroxides are preferred as bases.
  • the metal ion is preferably one selected from the group consisting of Zn (II), Ba (II), Sn (II), Pb (II), Mn (II), Co (II ), Ni (II), Fe (li), Cd (ll), Hg (ll), Pd (ll), Pt (ll).
  • the metal ion is Zn (II).
  • the metal ion is preferably used here as a salt with an anion, the corresponding acid of which has a pK a between 0 and 7, particularly preferably between 3 and 6 and / or whose pK a value is less than one unit from the pH of the one used Detergent deviates and / or it is an anion selected from the group consisting of halide, in particular fluoride, chloride or iodide, perchlorate, sulfate, amidosulfonate, diphosphonate, sulfite, nitrate and acetate and / or it is the anion of an organic carboxylic acid.
  • halide in particular fluoride, chloride or iodide, perchlorate, sulfate, amidosulfonate, diphosphonate, sulfite, nitrate and acetate and / or it is the anion of an organic carboxylic acid.
  • the organic carboxylic acid is preferably a monomeric and / or polymeric organic acid, the salts of monomeric and / or polymeric organic acids from the group of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymer carboxylic acids are preferred, and it it is further preferred that there are no salts of unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.
  • methanoic acid formic acid
  • ethanoic acid acetic acid
  • propanoic acid propanoic acid
  • pentanoic acid valeric acid
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic dodecanoic (lauric)
  • tridecanoic tetradecanoic
  • myristic pentadecanoic, hexadecanoic (palmitic acid
  • heptadecanoic acid margaric
  • octadecanoic acid stearic acid
  • eicosanoic acid arachidic acid
  • docosanoic acid behenic acid
  • tetracosanoic acid lignoceric acid
  • Hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid), 9c- hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t- octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t- Octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid).
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3.5 -Dicarboxybenzoic acid (trimesionic acid).
  • hydroxy acids hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2,3-dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 -Hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polymeric carboxylic acids polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone polyacrylic acid, vinyl acids, especially vinyl acrylates, and polyglutamic acid and copolymers of aspartic acid and glutamic acid.
  • the polymeric carboxylic acids here preferably have a molecular weight between 1000 and 50,000 Da (g mol "1 ), particularly preferably between 2000 and 6000 Da (g mol " 1 ).
  • the spectrum of the salts which can be used according to the invention ranges from salts which are sparingly soluble in water, ie have a solubility below 100 mg / l, to salts which have a solubility in water above 100 mg / l l, preferably above 500 mg / l, particularly preferably above 1 g / l (all solubilities at 20 ° C. water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of readily soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the cleaning agents according to the invention contain at least one zinc salt selected from the group consisting of zinc acetate, zinc sulfate, zinc formate and zinc lactate.
  • the cleaning agent further preferably contains at least one acid, preferably selected from the group consisting of halogen acids, in particular hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, acetic acid, phosphoric acid, amidosulfonic acid or one of the aforementioned organic acids.
  • sulfonic acid derivatives can be used as acids, both alkyl and aryl sulfonic acids being suitable. Benzene sulfonic acid, toluenesulfonic acid and cumene sulfonic acid are preferred.
  • the acids mentioned, based on the individual acids, are preferably present in the detergent in an amount of between 0.1 and 10% by weight, in particular between 2 and 6% by weight.
  • the salts of the acids in particular their alkali metal salts, can also be used.
  • an agent containing metal salts of metal ions which form sparingly soluble salts with carbonate in particular those mentioned above, which form carbonate salts which are less soluble than calcium carbonate, to a commercially available cleaning agent, in particular sanitary cleaning agent to add.
  • pretreatment with a neutral or slightly basic solution which contains salts of metal ions which form sparingly soluble salts with carbonate, in particular those mentioned above is carried out before the treatment with a cleaning agent according to the invention.
  • This pretreatment can be carried out especially for new, as yet untreated fittings.
  • the pretreatment can also precede each cleaning step in which a cleaner according to the invention is used.
  • the cleaning agent is preferably a liquid aqueous agent, but it can also be, for example, a gel, a paste or a powder. If it is a liquid agent, it preferably has a viscosity of up to 1000 mPas, in particular of up to 100 mPas.
  • gel-like or pasty cleaning agents can have viscosities of up to 150,000 mPas.
  • the viscosity measurements are carried out at 20 ° C in the Brookfield LVDV II viscometer with a rotor frequency of 20 rpm (spindle no. 31, conc. 100%).
  • the cleaning agent according to the invention preferably contains other constituents, as are customary for cleaning agents and in particular for sanitary cleaning agents.
  • the cleaning agent according to the invention can, for example, be additives selected from the group consisting of surfactants, builders, hydrogen peroxide, enzymes (in particular those which are suitable for breaking down biofilms), dyes, fragrances, acids, alkaline substances, hydrotropes, pH regulators, solvents, thickeners , Corrosion inhibitors, UV stabilizers, cleaning enhancers, pearlescent agents (for example glycol distearate), opacifiers, antistatic agents, polymers and skin protection agents (as described for example in EP 522 506). If the cleaning agent is to be sprayed, it may also contain a blowing agent. These ingredients are described as examples below.
  • preferred cleaning agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9 .i 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 - 1 8 monoolefins with an end or internal double bond by sulfonation gaseous sulfur trioxide and subsequent alkaline or acidic hy- drolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 2 .i8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the sulfuric acid monoesters of the straight-chain or branched C 2 -i alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9 .n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C- ⁇ 2 -i 8 fatty alcohols with 1 to 4 EO are suitable. They are found in detergents because of their high level Foaming behavior is used only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • non-ionic surfactants Another group of washing-active substances are the non-ionic surfactants.
  • nonionic surfactants which can be used are alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci 2 u alcohols with 3 EO or 4 EO, C 9 . ⁇ alcohol with 7 EO, C ⁇ 3 . 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 - ⁇ 8 - Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci 2 -i 4 alcohol with 3 EO and C ⁇ 2 -i8-A!
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • alkyl polyglycosides Another class of nonionic surfactants which are used with particular preference in accordance with the invention are the alkyl polyglycosides (APG).
  • Alkypolyglycosides which can be used have the general formula RO (-G) z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 8 to 18, C atoms, G represents a glycosidically bound residue of a monosaccharide and z is a value between 1 and 10.
  • a synthesis on the industrial scale which is important for the production of the APG consists essentially in the acid-catalyzed condensation of monosaccharides of the aldose type (HO-G) with long-chain alcohols (R-OH) which contain 8 to 22, preferably 8 to 18, C atoms contain.
  • Alkyl glycosides of the formula (I) are formed when water is released
  • RO (-G) 2 (I) the value of z can be varied within wide limits by the choice of the reaction conditions.
  • the following monosaccharides are preferably suitable as starting materials: glucose, mannose, galactose, arabinose, apiose, lyxose, gallose, altrose, idose, ribose, xylose and talose as well as the oligo- and polysaccharides composed of these monosaccharides, for example maltose, lactose, maltotriose, hemicellulose , Starch, partial hydrolyzates of starch and sugar syrup.
  • alkyl glycosides are preferred which are composed of the same monosaccharide units. Alkyl glycosides in which the rest (-G) is derived from glucose are particularly preferred.
  • glucose, maltose, starch and other oligomers of glucose are used accordingly as starting materials.
  • the alkyl part R is derived from the production of long-chain, optionally unsaturated, preferably primary alcohols described above, which may also be branched. Examples are the synthetic oxo alcohols with 9 to 15 C atoms and the fatty alcohols obtained from natural fatty acids with 8 - 22 C atoms. The fatty alcohols with 8 to 18 carbon atoms are preferred and the oxo alcohols with 11 to 15 carbon atoms, but especially the fatty alcohols with 8 to 10 carbon atoms or with 12 to 14 carbon atoms.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethylionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil.
  • An interesting natural antiseptic agent is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in the linden blossom oil and has a lily of the valley smell. Glycerol monolaurate has also proven itself as a bacteriostatic. The amount of these antimicrobial agents strongly depends on the effectiveness of the respective compound and can be up to 5% by weight.
  • blowing agents are usually blowing gases, in particular liquefied or compressed gases.
  • the choice depends on the product to be sprayed and the area of application.
  • compressed gases such as nitrogen, carbon dioxide or nitrous oxide, which are generally insoluble in the liquid cleaning agent, the operating pressure decreases with each valve actuation.
  • Liquefied gases (liquefied gases) as propellants which are soluble in the detergent or even act as a solvent, offer the advantage of constant operating pressure and even distribution, because the propellant evaporates in air and takes up several hundred times its volume.
  • blowing agents designated in accordance with INCI are suitable: butanes, carbon dioxides, dimethyl carbonates, dimethyl ethers, ethanes, hydrochlorofluorocarbon 22, hydrochlorofluorocarbon 142b, hydrofluorocarbon 152a, hydrofluorocarbon 134a, hydrofluorocarbon 227ea, isobutanes, isopentanes, nitrogen, nitrous oxides Pentanes, propanes.
  • Chlorofluorocarbons chlorofluorocarbons, CFCs
  • blowing agents are, however, preferably largely and in particular completely dispensed with because of their harmful effect on the atmosphere's ozone shield, which protects against hard UV radiation, the so-called ozone layer.
  • Liquid gases are gases that can be converted from gaseous to liquid at mostly low pressures and 20 ° C.
  • liquefied gases include the hydrocarbons - which are produced in oil refineries as by-products in distillation and cracking of petroleum and in gas processing for gasoline separation - propane, propene, butane, butene, isobutane (2-methylpropane), isobutene ( 2-methyl propene, isobutylene) and mixtures thereof.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers (pressurized gas containers; also referred to as a spray can), self-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a container made of transparent polyethylene or polyethylene terephthalate.
  • Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein as spray dispensers, all of which are referred to in this regard and the contents of which are hereby incorporated into them Registration is described.
  • Trigger spray dispensers and pump atomizers have the advantage over pressurized gas containers that no propellant has to be used.
  • the agent according to the invention is not atomized as an aerosol, but rather is metered as cleaning foam on the spray dispenser by means of suitable, particle-compatible attachments, nozzles, etc. (so-called “nozzle valves”).
  • the cleaner according to the invention is a cleaner, in particular a foam cleaner, with a pH of between 3.7 and 4.6, the zinc acetate, zinc formate, zinc sulfate, zinc citrate or zinc lactate or mixtures thereof an amount between 0.5 and 10% by weight, citric acid, acetic acid, formic acid, maleic acid, lactic acid, tartaric acid, malonic acid, polyacrylic acid, polyglutamic acid or polyaspartic acid or their salts or mixtures thereof in an amount between 1 and 10% by weight, at least one of the aforementioned nonionic surfactants, in particular alkyl polyglycosides, especially APG 220, in an amount between 0.1 and 10% by weight and optionally small amounts of a monohydric alcohol with 2 to 3 carbon atoms, in particular Contains ethanol, and optionally an alkyl sulfate.
  • the acids or their salts mentioned are preferably present in amounts of 0.5 to 10% by weight, especially 2 to 6% by
  • Example 1 Attack of the marble surface at pH 4 and. pH 5 depending on the Zn (II) concentration
  • Example 2 Descaling performance and surface attack compared to a conventional bathroom cleaner
  • the lime dissolving performance of a conventional bathroom cleaner with an acidic pH value was measured in comparison to the lime dissolving performance of the same bathroom cleaner with the addition of Zn (II).
  • the attack on the marble surface was determined optically based on the gloss of the surface.
  • marble slabs that were additionally treated with zinc acetate before cleaning with the Zn (II) -containing agent show less damage than marble slabs that did not undergo such pretreatment.
  • Table 1 Results of the XPS investigations to determine the Zn (II) content of marble surfaces that were treated with zinc (II) acetate-containing solutions of different concentrations for different periods of time.
  • the lime stains can best be removed with the commercially available acidic bathroom cleaner.
  • the lime removal is somewhat poorer, but still clearly better than with pure water and than with the gentle cleaner for marble with pH 7, with which hardly any lime stains could be removed.
  • Example 5 Investigation of the Damage to Carrara Marble Slabs Carrara marble slabs were alternatively treated 10 times with a commercially available acidic bath cleaner and with a solution containing Zn (II) according to the invention. While the commercial acid bath cleaner clearly damaged the marble (after 10 cleaning operations), the solutions 2-4 from example 4 did not attack the marble surface.
  • Example 6 Optimizing the descaling power of the cleaner
  • the recipes of the samples from Table 2 have a descaling power between 13 and 140 mg Ca / 1, so they have a significantly higher descaling power than water or a neutral cleaner.
  • Sokalan PA 20 (BASF, Germany) can be used as polyacrylic acid and Baypure DS 100 (Bayer, Germany) as polyaspartic acid.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides, ainsi que son utilisation. Ledit produit nettoyant, présentant un pH compris entre 2 et 6, contient des cations bivalents qui forment avec le carbonate des sels peu solubles. Ces sels de carbonate peu solubles présentent un produit de solubilité inférieur à celui du carbonate de calcium. Le Zn (II) est utilisé de préférence comme cation.
PCT/EP2004/008863 2003-08-14 2004-08-06 Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides WO2005017083A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10337805A DE10337805A1 (de) 2003-08-14 2003-08-14 Reiniger zur schonenden Behandlung säureempfindlicher Carbonat-haltiger Oberflächen
DE10337805.7 2003-08-14
DE10348153A DE10348153A1 (de) 2003-10-13 2003-10-13 Reiniger zur schonenden Behandlung säureempfindlicher Carbonat-haltiger Oberflächen
DE10348153.2 2003-10-13

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WO2005017083A1 true WO2005017083A1 (fr) 2005-02-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2212408A1 (fr) * 2007-11-01 2010-08-04 The Clorox Company Compositions acides de nettoyage
WO2013004302A1 (fr) * 2011-07-05 2013-01-10 Ecolab Inc. Nettoyant acide pour le marbre

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US4738876A (en) * 1985-06-05 1988-04-19 S. C. Johnson & Son, Inc. Stone surface treating methods and compositions
EP0748864A1 (fr) * 1995-06-12 1996-12-18 The Procter & Gamble Company Composition de nettoyage et procédé pour le nettoyage des surfaces delicates
EP0780465A1 (fr) * 1995-12-18 1997-06-25 The Procter & Gamble Company Composition de nettoyage et méthode de nettoyage de surfaces délicates
US5780111A (en) * 1997-09-09 1998-07-14 Thrower; John H. Method of cleaning and conditioning surfaces
US6034043A (en) * 1999-04-20 2000-03-07 Lever Brothers Company, Division Of Conopco, Inc. Mild antimicrobial liquid cleansing formulations comprising polyvalent cation or cations for improving an antimicrobial effectiveness
US6046146A (en) * 1999-05-24 2000-04-04 Colgate Palmolive Company Antibacterial liquid hand surface cleaning compositions comprising zinc salt
WO2002010323A1 (fr) * 2000-07-31 2002-02-07 S.C. Johnson & Son, Inc. Raitement de surface à faible production de résidus
US6482788B1 (en) * 2002-05-13 2002-11-19 Colgate-Palmolive Company Light duty liquid composition containing an acid and zinc chloride
US6544940B1 (en) * 2002-05-13 2003-04-08 Colgate-Palmolive Company High foaming, grease cutting light duty liquid composition containing zinc chloride
WO2004061068A1 (fr) * 2002-12-30 2004-07-22 The Procter & Gamble Company Composition d'aide au rinçage contenant un sel metallique hydrosoluble destinee a etre utilisee dans un lave-vaisselle automatique pour la protection contre la corrosion de la verrerie

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4738876A (en) * 1985-06-05 1988-04-19 S. C. Johnson & Son, Inc. Stone surface treating methods and compositions
EP0748864A1 (fr) * 1995-06-12 1996-12-18 The Procter & Gamble Company Composition de nettoyage et procédé pour le nettoyage des surfaces delicates
EP0780465A1 (fr) * 1995-12-18 1997-06-25 The Procter & Gamble Company Composition de nettoyage et méthode de nettoyage de surfaces délicates
US5780111A (en) * 1997-09-09 1998-07-14 Thrower; John H. Method of cleaning and conditioning surfaces
US6034043A (en) * 1999-04-20 2000-03-07 Lever Brothers Company, Division Of Conopco, Inc. Mild antimicrobial liquid cleansing formulations comprising polyvalent cation or cations for improving an antimicrobial effectiveness
US6046146A (en) * 1999-05-24 2000-04-04 Colgate Palmolive Company Antibacterial liquid hand surface cleaning compositions comprising zinc salt
WO2002010323A1 (fr) * 2000-07-31 2002-02-07 S.C. Johnson & Son, Inc. Raitement de surface à faible production de résidus
US6482788B1 (en) * 2002-05-13 2002-11-19 Colgate-Palmolive Company Light duty liquid composition containing an acid and zinc chloride
US6544940B1 (en) * 2002-05-13 2003-04-08 Colgate-Palmolive Company High foaming, grease cutting light duty liquid composition containing zinc chloride
WO2004061068A1 (fr) * 2002-12-30 2004-07-22 The Procter & Gamble Company Composition d'aide au rinçage contenant un sel metallique hydrosoluble destinee a etre utilisee dans un lave-vaisselle automatique pour la protection contre la corrosion de la verrerie

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2212408A1 (fr) * 2007-11-01 2010-08-04 The Clorox Company Compositions acides de nettoyage
EP2212408A4 (fr) * 2007-11-01 2011-04-20 Clorox Co Compositions acides de nettoyage
AU2008319172B2 (en) * 2007-11-01 2014-02-13 The Clorox Company Acidic cleaning compositions
WO2013004302A1 (fr) * 2011-07-05 2013-01-10 Ecolab Inc. Nettoyant acide pour le marbre

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