EP1141227B1 - Produit de nettoyage multiphase contenant des condensats d'acide naphthalinsulfonique- formaldehyde - Google Patents

Produit de nettoyage multiphase contenant des condensats d'acide naphthalinsulfonique- formaldehyde Download PDF

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Publication number
EP1141227B1
EP1141227B1 EP99965460A EP99965460A EP1141227B1 EP 1141227 B1 EP1141227 B1 EP 1141227B1 EP 99965460 A EP99965460 A EP 99965460A EP 99965460 A EP99965460 A EP 99965460A EP 1141227 B1 EP1141227 B1 EP 1141227B1
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weight
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composition
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quantities
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German (de)
English (en)
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EP1141227A1 (fr
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Thomas Möller
Heinz-Dieter Soldanski
Stefanie Küch
Jürgen Noglich
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention relates to multi-phase liquid cleaning agents with naphthalenesulfonic acid-formaldehyde condensate, which can be temporarily emulsified by shaking, and for Cleaning hard surfaces, especially glass, can be used, as well as a method for cleaning hard surfaces.
  • the cleaning agents for hard surfaces that are common today are usually aqueous preparations in the form of a stable solution or dispersion which contain, as essential active ingredients, surface-active substances, organic solvents and, if appropriate, complexing agents for the hardness constituents of water, abrasives and cleaning alkalis.
  • Detergents which are primarily intended for cleaning glass and ceramic surfaces, are often formulated as solutions of the active substances in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such agents can be found in German patent application 22 20 540 US patents 3,839,234 and 3,882,038 and in European patent applications 344 847 and 393 772nd
  • German Offenlegungsschrift 39 10 170 describes compositions serving as mouthwash for the desorption of bacteria from solid surfaces and living tissues, which are in the form of a 2-phase preparation and form a temporary oil-in-water emulsion of limited life when shaken, the aqueous Phase comprises about 50 to 97% by weight and the water-immiscible oil phase comprises about 3 to 50% by weight.
  • Essential to the invention is a content of about 0.003 to 2% by weight of an amphiphilic cationic agent, for example a cationic surfactant, in an amount which enables the formation of the oil-in-water emulsion, this emulsion after about 10 seconds to 30 minutes their education breaks down and separates.
  • Anionic surfactants impair the antibacterial effect. No other surfactants are mentioned.
  • the European patent application 0 195 336 describes in two embodiments (1) and (2) shaking emulsifiable care products for sensitive surfaces, in particular (1) plastic surfaces or (2) compact disc disks, which in addition to an aqueous phase also contain an organic phase , which consists of chlorofluorocarbon (CFRP) 1,1,2-trichloro-1,2,2-trifluoroethane.
  • the agents are also free of wax and contain in the aqueous phase (1) at least one surfactant and a water-soluble liquid silicone oil or (2) the triethanolamine salt of a C 10-12 -alkylsulfuric acid half-ester. No statement is made about the stability of the emulsion that can be generated by shaking.
  • the surfactant content is usually from 1 to 10% by weight, in particular from 2 to 8% by weight, but if necessary also above 10% by weight, preference being given to anionic surfactants, in particular those having a sulfate or sulfonate group are. Due to their environmentally harmful properties, especially in connection with the ozone hole, the use of CFRP should be reduced or better avoided.
  • Hair treatment agents in the form of a 2-phase system are known from German laid-open publications 195 01 184, '187 and ' 188 ( Henkel KGaA) , which have an oil phase and a water phase, the oil phase preferably being based on silicone oil, and briefly due to mechanical action are miscible.
  • Substantive polymers are, in particular, polycarboxylates such as poly (vinylpyrrolidone-coacrylic acid), but also poly (styrene sulfonate), cationic sugar and starch derivatives and block copolymers composed of ethylene oxide and propylene oxide, the latter in particular having less substantivity.
  • polycarboxylates such as poly (vinylpyrrolidone-coacrylic acid), but also poly (styrene sulfonate), cationic sugar and starch derivatives and block copolymers composed of ethylene oxide and propylene oxide, the latter in particular having less substantivity.
  • the object of the present invention was therefore to provide high-performance, storage-stable and easy-to-use agents for cleaning hard surfaces which show separate phases, can be emulsified for use, remain homogeneous during use and then form separate phases again and after application to the hard surface counteract the rain or fogging effect, ie bring about an anti- rain effect or anti-fogging effect.
  • the invention relates to a liquid multi-phase Detergent with at least two continuous phases, the at least one aqueous phase I and an aqueous phase which is immiscible with this aqueous phase has liquid phase II and temporarily convert to an emulsion by shaking can, and which contains at least one naphthalenesulfonic acid-formaldehyde condensate.
  • immiscible, non-aqueous phase means a phase which is not based on water as the solvent , in the non-aqueous phase II small amounts, based on phase II, of water of up to 10% by weight, usually not more than 5 wt .-%, can be contained in solution.
  • an agent according to the invention consists of a continuous aqueous Phase, which consists of the entire phase I, and a continuous not aqueous liquid phase, which consists of the entire phase II.
  • continuous phases of an agent according to the invention can also be parts of a contain another phase in emulsified form, so that in such an agent, for example Phase I is present in part as a continuous phase I, which is the continuous represents aqueous phase of the agent, and to a different extent than discontinuous Phase I is emulsified in the continuous non-aqueous phase II.
  • Phase II and The same applies to other continuous phases.
  • the invention relates to the use of at least one naphthalenesulfonic acid-formaldehyde condensate in a cleaning agent for hard surfaces to reduce the rain effect and / or the fogging effect.
  • the invention in a third embodiment relates to a method for reduction the rain effect and / or the fogging effect on one with a liquid Detergent treated hard surface, the surface with a minimum a liquid cleaning agent containing naphthalenesulfonic acid-formaldehyde condensate is treated in concentrated or diluted form.
  • the invention further relates to a method for cleaning hard surfaces, in particular glass, in which a cleaning agent according to the invention is temporarily converted into an emulsion by shaking, in amounts of 1.5 to 10 g per m 2 onto the surface to be cleaned, preferably by spraying, applied and this surface is then cleaned if necessary by wiping with an absorbent soft object.
  • a particular advantage of the present invention is that the inventive Naphthalenesulfonic acid-formaldehyde condensates also an anti-rain and an anti-fog effect is brought about.
  • the agents according to the invention are distinguished by an overall high storage stability. So are the individual phases in Stable for a long time without, for example, deposits being formed, and the conversion into a temporary emulsion remains reversible even after frequent shaking.
  • the physical form of the agent according to the invention eliminates the problem of Stabilization of an agent formulated as an emulsion per se on the outside.
  • the separation of ingredients in separate phases can also increase the chemical stability of the agent promote.
  • the agents according to the invention have excellent residue behavior on. Greasy residues are largely avoided, so that the The surface remains shiny without the need for rinsing.
  • the content of at least one naphthalenesulfonic acid-formaldehyde condensate in the The agent according to the invention is usually 0.001 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, particularly preferably 0.1 to 1.5% by weight and most preferably 0.15 to 0.5% by weight.
  • Naphthalenesulfonic acid-formaldehyde condensates are polycondensation products from Naphthalenesulfonic acid and formaldehyde, which according to the known methods of alkaline or acidic condensation can be produced.
  • naphthalenesulfonic acid- formaldehyde condensate includes the naphthalenesulfone at -formaldehyde condensates, ie the salts of naphthalenesulfonic acid-formaldehyde condensates.
  • Suitable salts are, for example, the alkali metal and alkaline earth metal salts, preferably the sodium, potassium, magnesium and calcium salts, and also the ammonium salts of the naphthalenesulfonic acid-formaldehyde condensates or mixtures thereof, in particular the sodium salts.
  • Suitable according to the invention are both high-molecular to low-molecular naphthalenesulfonic acid-formaldehyde condensates, the low condensates somewhat preferred are.
  • suitable naphthalenesulfonic acid-formaldehyde condensates are for example, under the trade name Lomar ® by the company. Henkel Corp., For example, the low molecular weight sodium salts Lomar® LS, Lomar ® PW, Lomar ® PWFA 40 and Lomar ® PL 4, the high molecular weight sodium salts Lomar ® D and Lomar ® D SOL, the potassium salt Lomar ® HP and the ammonium salt Lomar ® PWA, and under the trade name Tamol® from BASF AG, for example the low-condensates Tamol® NN 2901, Tamol® NN 7718, Tamol® NN 8906, Tamol ® NN 9104 , Tamol® NN 9401 (all sodium salts) and Tamol® NNA 4109 (ammonium salt) with a molecular weight in the range of about 6,500 g / mol, the medium condensates Tamol ® NMC 4001 and
  • the agent is essentially CFRP-free, ie the non-aqueous liquid phase II is not based on CFRP. Because of the negative environmental influences of these compounds, the agents according to the invention preferably contain no CFRP at all, although small amounts, based on the total agent, of up to about 5% by weight are still tolerable.
  • the continuous phases are I and II delimited from each other by a sharp interface.
  • phase I and II parts preferably 0.1 to 35% by volume, in particular 0.2 to 20 vol .-%, based on the volume of the respective continuous phase, the each other phase as a dispersant.
  • the continuous phase I or II reduced by the volume that distributes as a dispersant in the other phase is.
  • Agents in which phase I in amounts of 0.1 to 35 vol .-%, preferably 0.2 to 20 vol .-%, based on the volume of phase II, in phase II is emulsified.
  • a further preferred embodiment of the invention lies next to the continuous Phases I and II part of the two phases as an emulsion of one of the two phases in the other phase, this emulsion being separated by two sharp interfaces, an upper and a lower, compared to the parts of the Phases I and II are delimited.
  • the agents according to the invention preferably contain 5 to 95% by volume of phase I and 95 up to 5 vol% phase II.
  • the agent contains 35 to 95 vol .-% phase I and 5 to 65 vol .-% phase II, in particular 55 to 95 vol .-% phase I and 5 to 45% by volume of phase II, most preferably 70 to 95% by volume of phase I and 5 to 30 vol .-% phase II.
  • the continuous phase I is preferably the lower Phase and the continuous phase II the upper phase.
  • the water-immiscible phase II is based on aliphatic gasoline hydrocarbons and / or terpene hydrocarbons.
  • the petrol hydrocarbons preferably have a boiling point range from 130 to 260 ° C, in particular from 140 to 240 ° C, particularly preferably from 150 to 220 ° C, such as the C 9-13 isoparaffins with a boiling point range from 184 to 217 ° C, available for example as Shellsol ® T from Deutsche Shell Chemie AG (Eschborn).
  • Suitable terpene hydrocarbons are, for example, citrus oils such as the orange oil obtained from the peel of oranges, the orange terpenes contained therein, in particular limes, or pine oil, the pine oil extracted from roots and stumps.
  • Phase II can also consist exclusively of aliphatic gasoline hydrocarbons and / or terpene hydrocarbons.
  • Phase II contains gasoline hydrocarbons preferably in amounts of at least 60% by weight, particularly preferably 90 to 99.99% by weight, in particular 95 to 99.9% by weight, extremely preferably 97 to 99% by weight ,
  • Suitable surfactants for the agents according to the invention are surfactants, especially from the classes of anionic and nonionic surfactants.
  • the agents contain anionic and nonionic surfactants, the anionic Surfactants are contained in phase I in particular.
  • the amount of anionic surfactant is based on phase I, usually not more than 10 wt .-%, preferably between 0.01 and 5 wt .-%, in particular between 0.01 and 0.5 wt .-%, particularly preferred between 0.1 and 0.3% by weight.
  • the agents contain non-ionic surfactants their concentration, preferably in phase I, based on phase I, usually not over 3% by weight, preferably between 0.001 and 0.3% by weight and in particular between 0.001 and 0.1% by weight, and usually not in phase II, based on phase II over 5% by weight, preferably between 0.001 and 0.5% by weight and in particular between 0.001 and 0.2% by weight, particularly preferably between 0.005 and 0.1% by weight, most preferably between 0.01 and 0.05% by weight.
  • Suitable anionic surfactants are preferably C 8 -C 18 alkylbenzenesulfonates, in particular with about 12 C atoms in the alkyl part, C 8 -C 20 alkanesulfonates, C 8 -C 18 monoalkyl sulfates, C 8 -C 18 alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid esters with 8 to 18 carbon atoms in the alcohol residues.
  • EO ethylene oxide units
  • the anionic surfactants are preferably used as sodium salts, but can also as other alkali or alkaline earth metal salts, for example magnesium salts, and be contained in the form of ammonium or amine salts.
  • surfactants are sodium cocoalkyl sulfate, sodium sec-alkane sulfonate with approx. 15 carbon atoms and sodium dioctyl sulfosuccinate.
  • Fatty alkyl sulfates with 12 to 14 carbon atoms as well as sodium lauryl ether sulfate with 2 EO have been proven.
  • nonionic surfactants especially C 8 -C 18 alcohol polyglycol ethers, ie ethoxylated alcohols with 8 to 18 C atoms in the alkyl part and 2 to 15 ethylene oxide units (EO), C 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EO, ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides with 14 to 20 C atoms and long-chain alkyl polyglycosides with 8 to 14 C atoms in the alkyl part and 1 to 3 glycoside units.
  • EO ethylene oxide units
  • C 8 -C 18 carboxylic acid polyglycol esters with 2 to 15 EO
  • ethoxylated fatty acid amides with 12 to 18 C atoms in the fatty acid part and 2 to 8 EO
  • long-chain amine oxides with 14 to 20 C atoms
  • surfactants examples include oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, coconut alkyl dimethylamine oxide and coconut alkyl polyglucoside with an average of 1.4 glucose units.
  • nonionic surfactants in the aqueous phase in addition to the addition products from ethylene oxide and fatty alcohols with in particular 4 to 8 ethylene oxide units the alkyl polyglycosides, and of these in turn the representatives with 8 to 10 carbon atoms in the alkyl part and up to 2 glucose units.
  • fatty alcohol polyglycol ethers with in particular 2 to 8 EO for example Oleyl-cetyl alcohol + 5-EO ether
  • FSE fatty acid polyglycol ester
  • nonionic surfactants especially the alcohol polyglycol ethers and Carboxylic acid polyglycol esters, for phase II the degree of ethoxylation to the C chain length coordinated in such a way that shorter C chains with lower degrees of ethoxylation or longer C chains can be combined with higher degrees of ethoxylation.
  • Agents which contain anionic and nonionic surfactant are particularly preferred.
  • Combinations of anionic surfactant in phase I and nonionic surfactant in phase II are particularly advantageous, for example combinations of fatty alkyl sulfates and / or fatty alcohol polyglycol ether sulfates in phase I with fatty alcohol polyglycol ethers and / or FSE in phase II.
  • the cleaning agents according to the invention can be water-soluble organic Solvents in the form of lower alcohols and / or ether alcohols, but preferably Contain mixtures of alcohols and ether alcohols.
  • the amount of organic solvent is preferably 0.1 to 15% by weight, in particular 1 to 10% by weight, based on the aqueous phase I.
  • ethanol isopropanol and n-propanol are used as alcohols.
  • Ether alcohols are sufficiently water-soluble compounds with up to 10 C atoms in the molecule.
  • ether alcohols are 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.
  • the weight ratio is both preferably between 1: 2 and 4: 1 Invention ethanol preferred.
  • the agents can be converted into the temporary emulsion according to the invention by shaking preferably up to three times, in particular up to twice, particularly preferably once, the temporary emulsion generated by shaking over a period of time of about 0.5 to 10 minutes sufficient for convenient use of the agent , preferably 1 to 5 min, in particular 1.5 to 4 min, is stable, ie on the one hand does not collapse again immediately after the end of the pouring and on the other hand does not persist in the long term.
  • constant is to be understood to mean that, after the respective time, at least 90% by volume of the agent is still present as the temporary emulsion generated by shaking.
  • a regulation for setting the latter properties of the agents according to the invention consists in controlling the viscosity of the individual phases.
  • the aqueous phase I preferably has a Brookfield viscosity (model DV-II +, spindle 31, rotational frequency 20 min -1 , 20 ° C.) of 0.1 to 200 mPa ⁇ s, in particular 0.5 to 100 mPa ⁇ s, extremely preferably 1 to 60 mPa ⁇ s.
  • the agent or the phases it contains can contain viscosity regulators.
  • the amount of viscosity regulator in phase I, based on phase I, is usually up to 0.5% by weight, preferably 0.001 to 0.3% by weight, in particular 0.01 to 0.2% by weight, extremely preferred 0.05 to 0.15% by weight.
  • Suitable viscosity regulators include synthetic polymers such as the homo- and / or copolymers of acrylic acid or their derivatives, for example the products from Goodrich available under the trade name Carbopol® , in particular the crosslinked acrylic acid copolymer Carbopol® ETD 2623.
  • Carbopol® the products from Goodrich available under the trade name Carbopol®
  • Carbopol® ETD 2623 the crosslinked acrylic acid copolymer
  • WO 97 / 38076 lists a number of other polymers derived from acrylic acid, which are also suitable viscosity regulators.
  • the agents according to the invention can furthermore contain volatile alkali in phase I.
  • volatile alkali in phase I.
  • ammonia and / or alkanolamines which have up to 9 carbon atoms in the molecule may contain used.
  • the ethanolamines are preferred as alkanolamines and of these in turn the monoethanolamine.
  • the ammonia and / or alkanolamine content is, based on phase I, preferably 0.01 to 3 wt .-%, in particular 0.02 to 1% by weight, particularly preferably 0.05 to 0.5% by weight.
  • the agents according to the invention can additionally in phase I.
  • Contain carboxylic acid the equivalent ratio of amine and / or ammonia Carboxylic acid is preferably between 1: 0.9 and 1: 0.1.
  • Carboxylic acids are suitable with up to 6 carbon atoms, which are mono-, di- or polycarboxylic acids can.
  • the content of carboxylic acid is based on phase I, preferably between 0.01 and 2.7 wt .-%, in particular between 0.01 and 0.9% by weight.
  • carboxylic acids examples include acetic acid, Glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which preferably acetic acid, citric acid and lactic acid can be used. Especially acetic acid is preferably used.
  • the agent according to the invention Use and the inventive method is at least one Naphthalenesulfonic acid-formaldehyde condensate together with at least one other Additive used, which also reduces the rain and / or fogging effect causes.
  • This can be one or more water-soluble additives and / or to one or more additives which in an agent according to the invention are essentially dissolved in the non-aqueous phase II.
  • additives within the meaning of this particular embodiment which are essentially dissolved in an aqueous phase I in an agent according to the invention , are in particular (i) the substantive polymers with hydrophilic groups of WO 96/04358 A1 ( Procter & Gamble ), in particular polycarboxylates such as poly (vinylpyrrolidone-co-acrylic acid), but also poly (styrene sulfonate), cationic sugar and starch derivatives and block copolymers composed of ethylene oxide and propylene oxide, with an average molecular weight of 10,000 to 3,000,000 g / mol, preferably 20,000 to 2,500,000 g / mol mol, in particular 300,000 to 2,000,000 g / mol, extremely preferably 400,000 to 1,500,000 g / mol, (ii) the amine oxide polymers, in particular poly (4-vinylpyridine-N-oxides), of WO 97/33963 A1 ( Procter & Gamble ) with an average mo
  • alkoxylated dihydroxyaromatics of the formula A, in which X is a single bond, a C 1-5 alkylene group, a carbonyl group or a group CR 1 , where R 1 is a hydrogen atom or a C 1-6 alkyl group, Y is a single bond, a C 1-5 alkylene group, a carbonyl group, a group CR 2 , where R 2 is a hydrogen atom or a C 1-6 alkyl group, or two hydrogen atoms, where the group "-Y-" then corresponds to "-H H-", R is a hydrogen atom, a C 1-6 alkyl group or mixtures thereof, m represents a number from 0 to about 20 and n represents a number from 0 to about 20 and the sum m + n> 0.
  • each alkoxylated dihydroxyaromatic is based on its solubility in the non-aqueous phase II, preferably not more alkoxylated dihydroxyaromatic than is homogeneously soluble in the non-aqueous base of phase II.
  • Particularly preferred alkoxylated dihydroxyaromatics have a high solubility in aliphatic gasoline hydrocarbons which, as will be described below, represent a preferred basis for the non-aqueous phase II.
  • Suitable aromatic bases of the alkoxylated Dihydroxyaromatics, ie formula A without the groups H [OCH (R) CH 2 ] m O- and -O [CH2CH (R)] n H are, for example, biphenyl, diphenylmethane, 1,1-diphenylethane, 1,2-diphenylethane, 1,2-diphenylpropane, 1,3-diphenylpropane, 2,2-diphenylpropane, 1,2-diphenylbutane, 1,4-diphenylbutane, 2,2-diphenylbutane, 1,5-diphenylpentane, 3,3-diphenylpentane, fluorene, Fluorenone, anthracene and anthraquinone.
  • Known dihydroxyaromatics are, for example, the o, o'-biphenol and the bisphenols bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), bisphenol B (2,2-bis - (4-hydroxyphenyl) butane) and bisphenol F (2,2'-methylenediphenol).
  • the alkoxylation of the dihydroxyaromatics to give the alkoxylated dihydroxyaromatics of the formula A according to the invention is possible by known alkoxylation methods and is usually carried out under basic or acid catalysis at elevated temperatures and under elevated pressure, a normal or a narrowed homolog distribution being obtained, depending on the conditions selected.
  • n represents the average total degree of alkoxylation of the alkoxylated dihydroxyaromatics of the formula A according to the invention and assumes values in the range of real numbers from above 0 to approximately 40, m and n at the molecular level for corresponding integers from 0 to approximately 20 the respective homolog distribution.
  • the corresponding average degrees of alkoxylation m and n are generally the same, while m and n can be the same or different at the molecular level.
  • the average total degree of alkoxylation is preferably 0.1 to 30, in particular 0.5 to 25, particularly preferably 1 to 20 and extremely preferably 1.5 to 15.
  • These can be mixed alkoxylates with ethyleneoxy (EO) and propyleneoxy units (PO), preferably pure ethoxylates or in particular pure propoxylates.
  • dihydroxyaromatics of the formula A can also be used in which R represents an ethyl, propyl, isopropyl, butyl, sec butyl, tert- butyl, pentyl and / or hexyl radical.
  • Preferred alkoxylated dihydroxyaromatics of the formula A have as group "-Y-" two hydrogen atoms "-H H-” and carry the alkoxylated hydroxy groups in particular in the 4- and 4'-position (with respect to X) according to formula B, where -X- preferably a C 1-5 alkylene group -C (R 3 ) (R 4 ) -, in which R 3 and R 4 are H, CH 3 , CH 2 CH 3 or CH 2 CH 2 CH 3 , in particular one 2,2-propylene or 2,2-butylene group.
  • Alkoxylated bisphenols A of formula C are sold, for example, under the trade name Dianol® by Akzo Nobel , for example Dianol® 22, Dianol® 220, Dianol® 22 D, Dianol® 240 1, Dianol® 264, Dianol® 285, Dianol® 33, Dianol® 320, Dianol® 340 and Dianol® 33. and Dianol® 3130.
  • at least one naphthalenesulfonic acid-formaldehyde condensate together with at least one of the aforementioned water-soluble additives (i) to (vii) are used.
  • At least one naphthalenesulfonic acid-formaldehyde condensate together with at least one alkoxylated dihydroxyaromatic of formula A and at least one of the aforementioned water-soluble additives (i) to (vii) used.
  • the content of at least one of these further additives in an inventive is 0.001 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, particularly preferably 0.1 to 1.5% by weight and extremely preferably 0.15 up to 0.5% by weight.
  • the agents according to the invention can contain further auxiliaries Contain additives, as are common in such agents.
  • additives include in particular Dyes, perfume oils, pH regulators (e.g. citric acid, alkanolamines or NaOH), preservatives, complexing agents for alkaline earth ions, enzymes, bleaching systems and antistatic substances.
  • the amount of such additives is usually not over 2% by weight in the detergent.
  • the lower limit of the bet depends on the type of Additive from and can, for example, with dyes up to 0.001 wt .-% and below be.
  • the amount of auxiliaries is preferably between 0.01 and 1% by weight.
  • the pH of the aqueous phase I can be varied over a wide range, however, a range from 2.5 to 12, preferably 5 to 10.5, is preferred 7 to 10.
  • the agent according to the invention is sprayable and can therefore be used in a spray dispenser become.
  • Another object of the invention is accordingly a product containing an inventive Agent and a spray dispenser.
  • the spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers, 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 greater detail in WO 96/04940 ( Procter & Gamble) and the US patents cited therein for spray dispensers, all of which are referenced in this regard and the contents of which are hereby incorporated into this application.
  • the agents according to the invention are used in such a way that the agent temporarily converted into an emulsion by shaking in amounts of, for example, about 1.5 to 10 g per m 2 , preferably 3 to 7 g per m 2 , on the surface to be cleaned applies and immediately wipes these surfaces with an absorbent soft object and thereby cleans them.
  • the agents are preferably applied with the aid of suitable spray devices, in particular a spray dispenser or a product according to the invention, in order to achieve a distribution which is as uniform as possible. Sponges or cloths are primarily suitable for wiping, which can be rinsed out with water from time to time when treating larger areas.
  • the agents according to the invention are obtained by mixing the individual phases separately directly from their respective raw materials, subsequent merging and Mix the phases and finally stand the means to separate the temporary emulsion. They can also be mixed up immediately from their raw materials, then mixing and finally standing the Use to separate the temporary emulsion.
  • a component in a phase other than that to which the respective component is attributed or with those who have been introduced into the remedy are not completely insoluble, so can these others
  • Corresponding phase in the setting of solubility equilibria by diffusion Contain portions of the component in question are not completely insoluble, so can these others.
  • E1 to E3 according to the invention and comparative agent V1 were prepared by simply stirring the components according to Table 1 together.
  • E1 to E3 contained the naphthalenesulfonic acid-formaldehyde condensate Lomar® LS in different amounts, while V1 had no additive.
  • C 9-13 isoparaffins served as the aliphatic gasoline hydrocarbon. All agents had a pH of 10 and contained a clear and transparent aqueous phase I at the bottom and a creamy whitish non-aqueous phase II at the top in a phase I to phase II volume ratio of 80 to 20 and separated by a sharp interface.
  • aqueous phase I was slightly thickened by the polymer so that the temporary emulsions generated by shaking remained stable for about 3 minutes each, which was sufficient for the convenient application of the agent, and the phases were then separated again.
  • the treated mirror was held for 5 sec over a dish (28 cm ⁇ 50 cm ⁇ 4 cm) with 1.5 l of boiling water and immediately afterwards evaluated whether and how much the mirror was fogged up.
  • agents E1 to E3 according to the invention show both an anti-rain effect and an anti-fog effect.

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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)
  • Phenolic Resins Or Amino Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (26)

  1. Produit de nettoyage liquide à plusieurs phases avec au moins deux phases continues, qui possède au moins une phase aqueuse I ainsi qu'une phase II liquide non aqueuse et non miscible à cette phase aqueuse, le produit pouvant être converti par agitation temporairement en une émulsion, caractérisé en ce qu'il contient au moins un condensé d'acide naphthalène-sulfonique - formaldéhyde.
  2. Produit selon la revendication 1, caractérisé en ce qu' il contient au moins un condensé acide naphtalènesulfonique-formaldéhyde en une quantité allant de 0,001 à 20 % en poids, de préference de 0,01 à 10 % en poids, en particulier de 0,05 à 5 % en poids et d'une manière particulièrement préférée de 0,1 à 1,5 % en poids et d'une manière extrêmement préférée de 0,15 à 0,5 % en poids.
  3. Produit selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que les phases continues I et II sont délimitées l'une par rapport à l'autre, par une interface nette.
  4. Produit selon l' une quelconque des revendications 1 à 3, caractérisé en ce qu' une ou les deux phases continues I et II contiennent des parties dispersés de l' autre phase, de préférence de 0,1 à 35% en volume, en particulier de 0,2 à 20 % en volume, rapporté au volume des phases continues respectives.
  5. Produit selon l'une quelconque des revendications précédentes, caractérisé en ce que la phase I est mise en émulsion dans la phase II en quantité allant de 0,1 à 35 % en volume, de préférence de 0,2 à 20 % en volume rapporté au volume de la phase II.
  6. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    à côté des phases I et II, continues, une partie des deux phases se présentent sous forme d'émulsion d'une des deux phases dans l'autre phase, pour laquelle cette émulsion est séparée par deux interfaces nettes, l'une supérieure et l'autre inférieure vis-à-vis des parties qui ne prennent pas part à l'émulsion des phases I et II.
  7. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient de 35 à 95 % en volume de phase I ainsi que 5 à 65 % en volume de phase II, en particulier de 55 à 95 % en volume de phase I ainsi que 5 à 45 % en volume de phase II, d'une manière extrêmement préférée de 70 à 95 % en volume de phase I ainsi que de 5 à 30 % en volume de phase II.
  8. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient une phase II basée sur ou constituée d'hydrocarbures aliphatiques, de préférence ayant une zone d'ébullition de 130 à 260°C, et/ou d'hydrocarbures-terpènes, de préférence de l'essence d'orange et/ou de l'essence de pin.
  9. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient dans la phase II des hydrocarbures aliphatiques ayant une zone d'ébullition de 140 à 220°C, de préférence de 150 à 200°C, en quantités rapportées à la phase II, de 60 à 99,99 % en poids, de préférence de 90 à 99,99 % en poids, en particulier de 95 à 99,9 % en poids et d'une manière extrêmement préférée de 97 à 99 % en poids.
  10. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient un agent tensioactif anionique et/ou non ionique.
  11. Produit selon l'une quelconque des revendications précédentes, caractérisé en ce qu' il contient un agent tensioactif anionique choisi dans le groupe des (alkyl en C8-C18)benzénesulfonates, des (alkane en C8-C20)sulfonates, des mono(alkyl en C8-C18)sulfates, des éthersulfates de C8-C18 alkypolyglycol ayant de 2 à 6 éléments d'oxyde d'éthylène, ainsi que des esters d'alcool (alkylique en C8-C18) d'acide sulfosuccinique et leurs mélanges.
  12. Produit selon l'une quelconque de revendications précédentes, caractérisé en ce qu' il contient dans la phase I et/ou II un agent tensioactif non ionique choisi dans le groupe des éthoxylates d'alcool à chaíne plus longue, des alkylpolyglycosides et de leurs mélanges.
  13. Produit selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient un agent tensioactif anionique et non ionique.
  14. Produit selon l'une quelconque des reventdications précédentes, caractérisé en ce qu'il contient dans la phase I un agent tensioactif anionique en particulier des sulfates d'alcool gras en C12-C14 et/ou des sulfates d'éther d'alcool gras et de polyglycol ayant de préférence 2 éléments d'oxyde d'éthylène (OE) et dans la phase II un agent tensioactif non ionique, en particulier un éther d'alcool gras en C16-C18 et de polyglycol ayant de préférence de 2 à 8 OE et/ou un ester d'acide gras en C14-C18 et de polyglycol ayant de préférence de 2 à 10 OE.
  15. Produit selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient des solvants organiques solubles dans l'eau choisis dans le groupe des alcools inférieurs, ayant 2 ou 3 atomes de carbone, de l'éther monobutylique d'éthylèneglycol, de l'éther monobutylique de propylèneglycol, les derniers étant des éthers de glycol, ainsi que leurs mélanges.
  16. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient dans la phase I rapporté à la phase I de 0,1 à 15 % en poids, de préférence de 1 à 10 % en poids de solvant.
  17. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient dans la phase I un régulateur de viscosité, en particulier des homo- et/ou des copolymères d'acide acrylique ou de leurs sels, en quantités rapportées à la phase I de jusqu'à 0,5 % en poids, de préférence de 0,001 à 0,3 % en poids, en particulier de 0,01 à 0,2 % en poids, d'une manière particulièrement préférée de 0,05 à 15 % en poids.
  18. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient une phase I ayant une viscosité de 0,1 à 200 mPa.s, en particulier de 0,5 à 100 mPa.s et d'une manière extrêmement préférée de 1 à 60 mPa.s.
  19. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient dans la phase I un alcali volatil, en particulier de l'ammoniac et/ou une alkanolamine ayant jusqu'à 9 atomes de C, en quantités rapportées à la phase I, allant de 0,01 à 3 % en poids de préférence de 0,02 à 1 % en poids, en particulier de 0,05 à 0,5 % en poids.
  20. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient au moins un autre additif qui occasionne également une diminution de l'effet de pluie et/ou de l'effet de buée, de préférence au moins un produit dihydroxyaromatique au moins alkoxylé.
  21. Produit selon l'une quelconque des revendications précédentes,
    caractérisé en ce qu'
    il contient
    de 70 à 95 % en volume de phase aqueuse I contenant :
    de 0,01 à 10 % en poids d'agent tensioactif anionique,
    de 0 à 3 % en poids d'agent tensioactif non ionique,
    de 0,1 à 1,5 % en poids d'au moins un condensé d'acide naphtalènesulfonique-formaldéhyde,
    de 0 à 1,5 % en poids d'un autre additif soluble dans l'eau en vue de la diminution de l'effet de pluie et/ou de buée,
    de 0 à 10 % en poids de solvant organique soluble dans l'eau,
    de 0 à 0,5 % en poids d'un régulateur de viscosité,
    de 0 à 3 % en poids d'un alcali volatil,
    de 0 à 0,2 % en poids de parfum, et
       qsp. 100 % en poids d'eau, et
    de 5 à 30 % en volume de phase II non aqueuse contenant:
    de 0 à 100 % en poids d'hydrocarbures aliphatique,
    de 0 à 100 % en poids d'hydrocarbures terphéniques,
    de 0 à 5 % en poids d'au moins un composé dihydrocyaromatique alkoxylé de formule A,
    de 0 à 5 % en poids d'un agent tensioactif non ionique, et
    de 0 à 1 % en poids de parfum,
    des données en % en poids se rapportant à la quantité respective de la phase, la somme des hydrocarbures aliphatiques et terpéniques de la phase II se complète 100 % en poids, et les phases peuvent contenir en supplément de faibles les quantités de colorant.
  22. Produit selon la revendication précédente, caractérise en ce qu'il contient les agents tensioactifs anioniques en quantités allant de 0,01 à 5 % en poids de préférence de 0,01 à 0,5 % en poids, en particulier de 0,1 à 0,3 % en poids et les agents tensioactifs non ioniques en quantités allant de 0,001 à 0,5 % en poids, de préférence de 0,005 à 0,1 % en poids, en particulier de 0,01 à 0,05 % en poids.
  23. Procédé de nettoyage de surfaces dures en particulier le verre, dans lequel, un produit de nettoyage conformément à l'une des revendications précédentes est converti en une émulsion temporairement par agitation, appliqué en quantités allant de 1,5 à 10 g par m2 sur la surface à nettoyer de préférence par vaporisation on purifie ces surfaces en connexion avec cela, par frottement avec un objet doux absorbant.
  24. Procédé de diminution de l'effet de pluie et/ou de l'effet de buée sur une des surfaces dures traitées avec un produit de nettoyage liquide,
    caractérisé en ce que
    la surface est traitée avec un produit de nettoyage liquide contenant au moins un condensé acide naphtalènesulfonique-formaldéhyde sous forme concentrée ou diluée.
  25. Utilisation d'au moins un condensé acide naphtalènesulfonique-formaldéhyde dans un produit de nettoyage pour surfaces dures en vue de la diminution de l'effet de pluie et/ou de l'effet de buée.
  26. Article contenant une composition selon l'une quelconque des revendications de produit précédentes et un dispensateur de vaporisation.
EP99965460A 1998-12-23 1999-12-14 Produit de nettoyage multiphase contenant des condensats d'acide naphthalinsulfonique- formaldehyde Expired - Lifetime EP1141227B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19859778 1998-12-23
DE19859778A DE19859778A1 (de) 1998-12-23 1998-12-23 Mehrphasiges Reinigungsmittel mit Naphthalinsulfonsäure-Formaldehyd-Kondensat
PCT/EP1999/009891 WO2000039269A1 (fr) 1998-12-23 1999-12-14 Produit de nettoyage multiphase contenant des condensats d'acide naphthalinsulfonique- formaldehyde

Publications (2)

Publication Number Publication Date
EP1141227A1 EP1141227A1 (fr) 2001-10-10
EP1141227B1 true EP1141227B1 (fr) 2002-09-11

Family

ID=7892477

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99965460A Expired - Lifetime EP1141227B1 (fr) 1998-12-23 1999-12-14 Produit de nettoyage multiphase contenant des condensats d'acide naphthalinsulfonique- formaldehyde

Country Status (8)

Country Link
US (1) US6362154B1 (fr)
EP (1) EP1141227B1 (fr)
AT (1) ATE223964T1 (fr)
AU (1) AU2096800A (fr)
CA (1) CA2292436A1 (fr)
DE (2) DE19859778A1 (fr)
ES (1) ES2184518T3 (fr)
WO (1) WO2000039269A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1126019B1 (fr) * 1998-03-16 2003-06-04 Henkel Kommanditgesellschaft auf Aktien Utilisation d' une composition aqueuse multiphasique pour nettoyage des surfaces dures
DE19951635A1 (de) * 1999-10-26 2001-05-17 Henkel Kgaa Wäßriges mehrphasiges Reinigungsmittel
GB2372500B (en) * 2001-02-22 2003-08-20 Reckitt Benckiser Nv Process for Inhibition of Corrosion of Glassware during Automatic Dishwashing
DE10137047A1 (de) * 2001-07-31 2003-02-27 Henkel Kgaa Versprühbarer Reiniger, enthaltend eine tröpfchenförmige apolare Komponente
CN100531881C (zh) * 2001-08-13 2009-08-26 宝洁公司 新型低聚的疏水的分散剂和包括低聚的分散剂的衣物洗涤剂
US7448556B2 (en) 2002-08-16 2008-11-11 Henkel Kgaa Dispenser bottle for at least two active fluids
US8927473B2 (en) * 2011-12-30 2015-01-06 Walter Geslak Color indication of effectiveness of immiscible liquid suspension

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882038A (en) 1968-06-07 1975-05-06 Union Carbide Corp Cleaner compositions
US3696043A (en) 1970-10-21 1972-10-03 Dow Chemical Co Cleaning composition for glass and reflective surfaces
US3839234A (en) 1973-01-26 1974-10-01 C Roscoe Multi-purpose cleaning concentrate
DE2848447C3 (de) * 1977-11-10 1981-12-17 CIBA-GEIGY AG, 4002 Basel Färbeverfahren
US4302348A (en) * 1980-09-23 1981-11-24 The Drackett Company Hard surface cleaning compositions
DE3509090A1 (de) 1985-03-14 1986-09-18 Hoechst Ag Pflegemittel fuer kunststoff-oberflaechen
JPS61264099A (ja) * 1985-05-17 1986-11-21 花王株式会社 染色機器用洗浄剤
JPS62288605A (ja) * 1986-06-06 1987-12-15 Kanegafuchi Chem Ind Co Ltd 重合器内部の洗浄方法
IL85934A (en) 1988-03-30 1992-02-16 Univ Ramot Composition for desorbing bacteria containing amphipathic cations
US4943392A (en) 1988-06-03 1990-07-24 The Procter & Gamble Company Containing butoxy-propanol with low secondary isomer content
GB8824110D0 (en) * 1988-10-14 1988-11-23 Unilever Plc Liquid cleaning products
GB2228944A (en) * 1989-03-08 1990-09-12 Unilever Plc Non-aqueous liquid cleaning composition
GB8909157D0 (en) 1989-04-21 1989-06-07 Procter & Gamble Hard-surface cleaning compositions
GB9415904D0 (en) 1994-08-05 1994-09-28 Unilever Plc Process for the production of detergent composition
DE19501188A1 (de) 1995-01-17 1996-07-18 Henkel Kgaa 2-Phasen-Haarbehandlungsmittel III
DE19501184A1 (de) 1995-01-17 1996-07-18 Henkel Kgaa 2-Phasen-Haarbehandlungsmittel II
DE19501187A1 (de) 1995-01-17 1996-07-18 Henkel Kgaa 2-Phasen-Haarbehandlungsmittel I
US5726139A (en) 1996-03-14 1998-03-10 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics containing amine oxide polymers functionality
US5798324A (en) 1996-04-05 1998-08-25 S.C. Johnson & Son, Inc. Glass cleaner with adjustable rheology

Also Published As

Publication number Publication date
EP1141227A1 (fr) 2001-10-10
DE59902700D1 (de) 2002-10-17
AU2096800A (en) 2000-07-31
US6362154B1 (en) 2002-03-26
ES2184518T3 (es) 2003-04-01
CA2292436A1 (fr) 2000-06-23
WO2000039269A1 (fr) 2000-07-06
ATE223964T1 (de) 2002-09-15
DE19859778A1 (de) 2000-06-29

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