EP1869152B1 - Composition de nettoyage liquide destinee a une surface dure - Google Patents

Composition de nettoyage liquide destinee a une surface dure Download PDF

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Publication number
EP1869152B1
EP1869152B1 EP06707490A EP06707490A EP1869152B1 EP 1869152 B1 EP1869152 B1 EP 1869152B1 EP 06707490 A EP06707490 A EP 06707490A EP 06707490 A EP06707490 A EP 06707490A EP 1869152 B1 EP1869152 B1 EP 1869152B1
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EP
European Patent Office
Prior art keywords
composition
malonic acid
hard surface
cleaning
compositions
Prior art date
Legal status (The legal status 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 status listed.)
Not-in-force
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EP06707490A
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German (de)
English (en)
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EP1869152A1 (fr
Inventor
Alexander Thomas Ashcroft
David William Thornthwaite
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to EP06707490A priority Critical patent/EP1869152B1/fr
Priority to PL06707490T priority patent/PL1869152T3/pl
Publication of EP1869152A1 publication Critical patent/EP1869152A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C11D2111/14—

Definitions

  • the present invention relates to methods for cleaning hard surfaces, and to compositions suitable for that purpose, involving the application of malonic acid to such surfaces.
  • Household surfaces are normally cleaned using compositions which contain one or more ingredients which assist in removal of fatty/oily/greasy soil and/or any visible staining such as from associated solid debris.
  • Such compositions may be applied as diluted or concentrated aqueous solutions e.g. with a cloth, wipe or other implement or as a spray, such as a trigger spray dispenser or other aerosol applicator, optionally followed by rinsing.
  • compositions may be either acidic or alkaline.
  • Acidic compositions often contain carboxylic acids which may be mono-, di- or polycarboxylic acids, such as citric acid, sorbic acid, acetic acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid and glycolic acid. Unless the type of soil specifically requires the presence of a strong mineral acid, such acids are generally not recommended because of the damage they may cause on delicate and acid-sensitive surfaces.
  • Acidic cleaners are generally used for removing acid sensitive soil, such as limescale. For removal of fatty soil alkaline compositions are generally preferred.
  • WO00/32737 and WO00/27983 a cleaning process is described, using acids with pKa>3.5, to prevent damage to enamel surfaces.
  • Malonic acid is an optional ingredient in the composition and is described as chelating agent. Although the pKa of malonic acid is 2.8, no reference is made to that fact.
  • machine dish washing compositions comprising bicarboxylic acids, such as malonic acid, for corrosion inhibition.
  • the present invention provides a method for removing soil or stains from a hard surface as described in claim 6.
  • the present invention further provides a liquid hard surface cleaning composition according to claim 1.
  • soil and stain as used herein generally comprise all kinds of soils and stains generally encountered in the household, either of organic or inorganic origin, whether visible or invisible to the naked eye, including soiling solid debris and/or with bacteria or other pathogens.
  • the method and compositions according to the invention may be used to treat fatty or greasy soil and stains, more specifically those caused by natural fat or oil.
  • malonic acid exerts its effect by depositing on the surface and exerting an influence on soil or stains subsequently depositing on the surface such that such soil or stains are prevented from getting strongly attached to that surface.
  • a compound according to formula 1 (hereinafter briefly referred to as "malonic acid”) is applied to the surface as a solution, preferably an aqueous solution, which is thereafter left to dry on the surface.
  • Step (c) of the method is advantageously effected using a hard surface cleaning composition comprising malonic acid again so that soil or stain is removed and new malonic acid is applied, effectively constituting step (a) of a subsequent process according to the first aspect of the invention.
  • Step (c) is optionally followed by a rinsing step, preferably with water.
  • Malonic acid proper may be derived from sugar beet and can therefore be classified as a natural material, something that is increasingly important to present day consumers.
  • malonic acid is meant to include malonic acid derivatives and salts or mixtures of these compounds as defined above by formula 1.
  • R is selected from -H or -CH 3 or -CH 2 CH 3 .
  • the present invention may also deliver other benefits such as improved surface feel (e.g. smoothness) during and/or after cleaning, olfactory benefits (e.g. reduction in rancid odour) before cleaning, less surface corrosion and less noise during cleaning.
  • Further aspects of the present invention comprise use of compositions containing malonic acid, for obtaining one or more of these other benefits in a hard surface cleaning operation and/or use of malonic acid in the manufacture of products for delivering one or more such other benefits.
  • malonic acid does not discolour, which is a particular advantage for a cleaning method according to the invention.
  • compositions and articles according to the present invention are useful for treating any household surface such as found in kitchens and bathrooms, including cooker tops, extractor fans, tiles, floors, baths, toilets, wash basins, showers, dishwashers, taps, sinks, work surfaces.
  • These surfaces may, for example, be made of plastics, glass, enamel, ceramic, wood (painted, lacquered or otherwise) or metal (eg. stainless steel or chrome).
  • Malonic acid is applied to the surface in the form of a composition containing malonic acid or by means of a wipe impregnated with a composition containing malonic acid.
  • the composition must be suitable for depositing malonic acid material onto a hard surface.
  • Malonic acid may be present in the composition in any suitable form, for example in the form of a solution or dispersion.
  • liquid includes solutions, dispersions, emulsions, gels, pastes and the like. In liquid form, they preferably have a pH above 6.
  • Suitable liquid compositions include solutions, dispersions or emulsions in a liquid carrier, which may be an organic solvent or water or a combination thereof. Preferably the solvent is predominantly (i.e. 50% or more) water.
  • the compositions may be used only to deposit malonic acid, or they may have additional functions such as cleaning.
  • the total malonic acid compound of any such composition is at least 0.01%, more preferably at least 0.1%, and not more than 10%, preferably not more than 5%, more preferably not more than 2% of that composition and suitably not more than 1% of that composition.
  • the composition may be applied by any suitable means in diluted or concentrated form.
  • it can be poured or sprayed onto the surface from a container or from an aerosol can or from a spray gun applicator.
  • it may be applied using a cloth, wipe or other implement which has been wetted with the composition.
  • compositions for use in the present invention may include ingredients well known for use in hard surface cleaning compositions.
  • the hard surface cleaning compositions of the invention comprise at least a surfactant material, wherein the surfactant comprises anionic and nonionic surfactant, a polymer and optional other hard surface cleaning components.
  • the composition is a "liquid” having a viscosity of at least 100 mPa ⁇ s as measured at a shear rate of 21s -1 at room temperature, but preferably no more than 5,000 mPa ⁇ s.
  • This viscous liquid composition may be in the form of a viscous liquid per se, or a gel, foam, mousse or paste.
  • the viscosity may be due to one or more other components in the system, for example an "external polymeric thickener", which may be a synthetic polymer, e.g. of the polycarboxylate type such as Carbopol TM , or a natural polysaccharide gum such as xanthan gum or guar gum.
  • an "internal structuring” system may be used, employing one or more surfactants and optionally electrolyte, to create an ordered or liquid crystalline phase within the composition.
  • Foams and mousses are normally supplied from a dispenser which gassifies or aerates the product dispensed therefrom.
  • the pH of the composition is preferably above 6, more preferably at least 6.5, and not more than 14, preferably not more than 13, more preferably not more than 12.
  • the pH is preferably at least 7.
  • the pH of the solution may be adjusted with organic or inorganic acids or bases.
  • Preferred inorganic bases are preferably alkali or alkaline earth hydroxides, ammonia, carbonates or bicarbonates.
  • the alkali metal preferably being Sodium (Na + ) or Potassium (K + ) or the alkaline earth metal preferably being Calcium (Ca 2+ ) or Magnesium (Mg 2+ ).
  • the organic bases are preferably amine oxides.
  • Inorganic acids may include hydrochloric acid, sulphuric acid or phosphoric acid, and organic acids may include acetic acid, citric acid or formic acid as well as dicarboxilic acid mixtures such as Radimix (trade mark, Radici Group) and Sokalan DCS (trade mark, BASF).
  • compositions according to, or for use in, the invention comprise surfactants (detergent actives) which are chosen from both anionic and nonionic detergent actives.
  • the composition may further comprise cationic, amphoteric and zwitterionic surfactants.
  • the total amount of surfactant to be employed will be from 0.01 to 50%.
  • the amount is at least 0.1%, more preferably at least 0.5%, still more preferably at least 1%.
  • the maximum amount is usually 30% or less, preferably not more than 20%, or even at or below 10%.
  • Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulphuric acid mono-esters and sulphonic acids which have in the molecular structure a branched or straight chain alkyl group containing from 6 to 22 carbon atoms in the alkyl part.
  • anionic surfactants water soluble salts of:
  • the preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene- sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalen
  • the amount present in the compositions of the invention will generally be at least 0.1%, preferably at least 0.5%, more preferably at least 1.0%, but not more than 20%, preferably at most 10%, more preferably at most 8%.
  • a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
  • the length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.
  • Particular examples include:
  • the amount of nonionic surfactant to be employed in the cleaning composition of the invention will preferably be at least 0.1%, more preferably at least 0.5%, most preferably at least 1%.
  • the amount is suitably at most 15%, preferably not more than 10% and most preferably not more than 7%.
  • compositions may contain amounts of both anionic and nonionic surfactants which are chosen, bearing in mind the level of electrolyte if present, so as to provide a structured liquid detergent composition, i.e. one which is 'self-thickened'.
  • a structured liquid detergent composition i.e. one which is 'self-thickened'.
  • the weight ratio of anionic surfactant to nonionic surfactant may vary, taking the above considerations in mind, and will depend on their nature, but is in the range of from 20:1 to 1:10, preferably from 15:1 to 1:5, and ideally above 10:1 to 1:2.
  • the compositions may comprise from 0.1.% to 7% by weight of malonic acid, from 0 to 20%, preferably from 0.5% to 10% by weight of water-soluble, synthetic anionic sulphate or sulphonate surfactant salt containing an alkyl radical having from 8 to 22 carbon atoms in the molecule, and from 0.5 to 7% by weight of ethoxylated nonionic surfactant derived from the condensation of an aliphatic alcohol having from 8 to 22 carbon atoms in the molecule with ethylene oxide, such that the condensate has from 2 to 15 moles of ethylene oxide per mole of aliphatic alcohol, the balance being the polymer, other optional ingredients and water.
  • amphoteric, cationic or zwitterionic surfactants in the compositions according to the invention.
  • Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane-sulphonate and sodium N-2-hydroxy-dodecyl-N-methyltaurate.
  • Suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl groups of from 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltrimethylammonium bromide.
  • a specific group of surfactants are the tertiary amines obtained by condensation of ethylene and/or propylene oxide with long chain aliphatic amines.
  • the compounds behave like nonionic surfactants in alkaline medium and like cationic surfactants in acid medium.
  • Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular C 12 -C 16 alkyl betaine, 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulphonate betaine, 3-(dodecylmethyl-sulphonium)-propane-1-sulphonate betaine, 3-(cetylmethyl-phosphonium)-propane-1-sulphonate betaine and N,N-dimethyl-N-dodecyl-glycine.
  • betaines are the alkylamidopropyl betaines e.g. those wherein the alkylamido group is derived
  • surfactants are compounds commonly used as surface-active agents given in the well-known textbooks: “ Surface Active Agents” Vol.1, by Schwartz & Perry, Interscience 1949 ; “ Surface Active Agents” Vol.2 by Schwartz, Perry & Berch, Interscience 1958 ; the current edition of “ McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company ; “ Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • compositions according to the present invention may include abrasives. However, these are generally not preferred as abrasives tend to damage or remove the thin layer of malonic acid being deposited on the surface.
  • the compositions may contain other ingredients which aid in their cleaning performance. For example, they may contain detergent builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates (especially ortho-, pyro- or polyphosphates or mixtures thereof), zeolites and mixtures thereof in an amount of up to 25%. Some of these builders can additionally function as abrasives if present in an amount in excess of their solubility in water. If present, the builder preferably will form at least 0.1% of the composition.
  • Metal ion sequestrants such as ethylenediaminetetraacetate or diethylenetriaminepentaacetate, amino-polyphosphonates (DEQUEST [TM] ) and phosphates and a wide variety of polyfunctional organic acids and salts, can also optionally be employed provided they are compatible with malonic acid.
  • DEQUEST [TM] amino-polyphosphonates
  • phosphates and a wide variety of polyfunctional organic acids and salts, can also optionally be employed provided they are compatible with malonic acid.
  • a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in compositions which have a tendency to produce excessive suds in use.
  • a suds regulating material which can be employed in compositions which have a tendency to produce excessive suds in use.
  • Soaps are salts of fatty acids and include alkali metal soaps such as the sodium, potassium and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from palm oil, coconut oil and ground nut oil. When employed, the amount of fatty acid or soap can form at least 0.005%, preferably 0.1% to 2% by weight of the composition. Commercially available fatty acid mixtures such as Prifac 7901 [TM] have been found to be suitable for this purpose.
  • hydrocarbon co-solvent may itself provide some or all of the required antifoaming activity.
  • compositions according to the invention may also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • composition of the inventions comprises polymers, in particular polymers that aid the binding of Malonic acid to the surface and thus providing additional rinse resistance.
  • Preferred polymers are nonionic and anionic polymers.
  • the polymer/malonic acid ratio (by weight) is in the range 1:1 to 20:1, preferably in the range 2:1 to 15:1, most preferably in the range 3:1 to 10:1.
  • Preferred polymers are those polymers having an average molecular weight above 4,000 Dalton. More preferably the molecular weight is at least 10,000 D, even more preferably above 100,000 D or even above 1,000,000 D. The polymers normally have a molecular weight below 5,000,000 Dalton, preferably below 4,000,000 D.
  • Suitable polymers are either water-soluble or water-dispersible, preferably water-soluble.
  • the non-ionic polymer may be chosen from cellulose-based nonionic polymers such as celluloses, alkylcelluloses, hydroxyalkylcelluloses, cellulose ethers, cellulose esters and cellulose amides, such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose.
  • cellulose-based nonionic polymers such as celluloses, alkylcelluloses, hydroxyalkylcelluloses, cellulose ethers, cellulose esters and cellulose amides, such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose.
  • Other polysaccharide polymers such as starches and modified starches, and dextrins, such as maltodextrin, are also suitable.
  • the polymer may be chosen from fully synthetic polymers such as polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene glycols such as polyethylene glycol, polyalkylene oxides, polyamides, polyacrylamides, polyvinylethers such as polymethylvinylether, polyvinyl acetates, and copolymers thereof.
  • fully synthetic polymers such as polyvinyl alcohols, polyvinylpyrrolidones, polyalkylene glycols such as polyethylene glycol, polyalkylene oxides, polyamides, polyacrylamides, polyvinylethers such as polymethylvinylether, polyvinyl acetates, and copolymers thereof.
  • Polyacrylic acids, polymethacrylic acids and their homologues, and other polycarboxylic acids may also be used in compositions where the polymers behave as nonionic polymers.
  • Such compositions are typically acidic compositions with pH values below about 4.
  • non-ionic polymer is selected from polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA) and combinations thereof.
  • compositions preferably comprise at least 0.1%, more preferably at least 0.5% by weight non-ionic polymer and at most 20%, preferably at most 10%, more preferably at most 5%.
  • the PVP includes substituted and unsubstituted vinyl pyrrolidone polymerization products
  • Preferred anionic polymers are water soluble anionic polymers.
  • Suitable polymers are mainly synthetic, but natural or nature-derived polymers may also be used.
  • Suitable polymers include polyacrylic acids and polymethacrylic acids and their homologues, other polycarboxylic acids, polyaminoacids or peptides, polyanhydrides, polystyrene sulphonic acids, polyvinylsulfonic acids, and their copolymers and their copolymers with nonionic monomers and polymers.
  • Natural gums such as xanthan, locust bean and carrageenans, and cellulose derivatives, such as carboxymethylcellulose, may also be suitable.
  • compositions preferably comprise at least 0.1%, more preferably at least 0.5% by weight anionic polymer and at most 20%, preferably at most 10%, more preferably at most 5%.
  • Liquid compositions may be stored in and dispensed by any suitable means, but spray applicators are particularly preferred. Pump dispensers (whether spray or non-spray pumps) and pouring applicators (bottles etc) are also possible.
  • the present invention provides a container for a liquid hard surface cleaner, the container comprising a reservoir containing malonic acid solution or a liquid composition having a pH above 6 and comprising malonic acid, and spray dispenser for dispensing the composition in the form of a spray.
  • the spray dispenser is preferably a trigger spray but may be any mechanical means for ejecting the liquid in spray or aerosol form.
  • Wipes can be impregnated with neat malonic acid or with a composition containing malonic acid.
  • the material may be impregnated dry, or more preferably in wet form (i.e. as a thin or a viscous liquid).
  • Suitable wipes include woven or nonwoven cloths, natural or synthetic sponges or spongy sheets, "squeegee” materials and the like.
  • the present invention provides a wipe impregnated with malonic acid or a composition containing malonic acid, such as any composition as defined or described elsewhere in this specification.
  • test surface a 5 by 5 cm area of standard stainless steel tiles are used.
  • the tiles are degreased prior to soiling using powdered calcite applied with a damp cloth.
  • Pretreatment is done by applying an evenly spread layer of 0.08 ml of the pretreatment composition to the target area of the tile.
  • the soil material used in the examples is Castor oil (ex John L. Seaton, Ref 9725).
  • the castor oil is used as received.
  • Castor oil is applied to the target area as an even film.
  • the tiles are then baked in an oven at 100°C for one hour.
  • the tile is then weighed to ensure that the target amount of 0.04 +/- 0.004g) of oil is on the tile.
  • the cleaning is carried out using a Martindale (trade mark, SDL International) abrasion instrument.
  • the tile to be cleaned is placed in the "holder” for the Martindale machine, and submerged under 20g of cleaning fluid.
  • a Ballerina cloth is fastened to the cleaning head of the Martindale machine, and this is rubbed across the surface of the tile using a pre-set pattern covering the whole tile. In the examples below the pattern is repeated three times for each application.
  • the tiles are rinsed under running water to remove excess cleaning product. The tiles are then left to dry in air
  • Example 1 and comparative example A.
  • compositions of Table 1 are used.
  • compositions of Table 3 are used.
  • degreased tiles are first pretreated with the one of the compositions of Table 4.
  • the tiles are left to dry for 15 minutes and rinsed with 300 ml of water, poured gently from a beaker.
  • compositions 4, 5 and 6 are used respectively.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Claims (10)

  1. Composition de nettoyage liquide pour surface dure comprenant :
    (a) de 0,01 à 10 % en poids d'acide malonique, de dérivés d'acide malonique et leurs sels de la formule
    Figure imgb0004
     dans laquelle A et A' sont choisis indépendamment parmi -H, des ions métalliques alcalins et alcalino-terreux, des ions quaternaires d'ammonium, des ions métalliques trivalents et des cations organiques, et dans laquelle R est choisi parmi -H ou alkyle en C1-C4 ou une combinaison de ces composés ;
    (b) de 0,01 à 50 % en poids de la composition totale de matériau tensioactif, dans laquelle le tensioactif comprend un tensioactif anionique et non-ionique dans un rapport compris entre 20:1 et 1:10 ; et
    dans laquelle la composition comprend en outre un polymère, le rapport polymère/acide malonique (en poids) devant être dans la plage de 1:1 à 20:1.
  2. Composition de nettoyage liquide pour surface dure selon la revendication 1 ayant un pH supérieur à 6.
  3. Composition de nettoyage liquide pour surface dure selon les revendications 1 ou 2, dans laquelle le tensioactif non-ionique est présent dans une concentration inférieure à 7 % en poids.
  4. Composition de nettoyage liquide pour surface dure selon l'une quelconque des revendications 1 à 3, dans laquelle R est -H, -CH3 ou -CH2CH3.
  5. Composition de nettoyage liquide pour surface dure selon l'une quelconque des revendications 1 à 4, dans laquelle A et A' sont choisis indépendamment parmi -H, NA+, K+, CA2+, NH4 + ou Mg2+.
  6. Méthode d'élimination de salissure ou de taches d'une surface dure, la méthode comprenant les étapes consistant en séquence à :
    (a) traiter la surface avec la composition selon l'une quelconque des revendications 1 à 5 ;
    (b) laisser la salissure ou la tache se déposer ; et
    (c) nettoyer la surface pour éliminer la salissure ou les taches.
  7. Méthode selon la revendication 6 dans laquelle la salissure ou la tache est une salissure ou tache grasse.
  8. Récipient destiné à contenir un nettoyant liquide pour surface dure, le récipient comprenant un réservoir contenant la composition de nettoyage selon l'une quelconque des revendications 1 à 5 et un distributeur pulvérisateur destiné à distribuer ladite composition sous la forme d'une pulvérisation.
  9. Récipient selon la revendication 8, dans lequel le distributeur pulvérisateur est un pulvérisateur à gâchette.
  10. Lingette imprégnée avec le nettoyant liquide pour surface dure selon l'une quelconque des revendications 1 à 5.
EP06707490A 2005-04-13 2006-03-09 Composition de nettoyage liquide destinee a une surface dure Not-in-force EP1869152B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06707490A EP1869152B1 (fr) 2005-04-13 2006-03-09 Composition de nettoyage liquide destinee a une surface dure
PL06707490T PL1869152T3 (pl) 2005-04-13 2006-03-09 Kompozycja do czyszczenia twardych powierzchni

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05252305 2005-04-13
EP06707490A EP1869152B1 (fr) 2005-04-13 2006-03-09 Composition de nettoyage liquide destinee a une surface dure
PCT/EP2006/002174 WO2006108475A1 (fr) 2005-04-13 2006-03-09 Composition de nettoyage liquide destinee a une surface dure

Publications (2)

Publication Number Publication Date
EP1869152A1 EP1869152A1 (fr) 2007-12-26
EP1869152B1 true EP1869152B1 (fr) 2009-08-26

Family

ID=34940806

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06707490A Not-in-force EP1869152B1 (fr) 2005-04-13 2006-03-09 Composition de nettoyage liquide destinee a une surface dure

Country Status (13)

Country Link
EP (1) EP1869152B1 (fr)
JP (1) JP2008535981A (fr)
CN (1) CN101160384B (fr)
AR (1) AR053210A1 (fr)
AT (1) ATE440937T1 (fr)
AU (1) AU2006233523B2 (fr)
BR (1) BRPI0607911A2 (fr)
CA (1) CA2602377C (fr)
DE (1) DE602006008761D1 (fr)
PL (1) PL1869152T3 (fr)
RU (1) RU2399655C2 (fr)
WO (1) WO2006108475A1 (fr)
ZA (1) ZA200708739B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8626216B2 (en) 2005-10-31 2014-01-07 Ntt Docomo, Inc. Transmission and reception bandwidth setting method, mobile terminal and base station in radio communication system that defines a plurality of signal bandwidths

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7741265B2 (en) 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
BRPI0911361A2 (pt) * 2008-04-04 2016-11-01 Unilever Nv uso de ácido cítrico e/ou citratos e método para remoção de resíduos ou manchas de superfícies rígidas.
CA2770127C (fr) 2009-08-06 2018-01-02 Arkema Inc. Compositions de nettoyage liquides
EP2305785A1 (fr) 2009-10-02 2011-04-06 Unilever N.V. Utilisation d'un composé carboxylique ou amino en tant qu'aide au nettoyage pour les surfaces dures et procédé de nettoyage desdites surfaces dures
EA024738B1 (ru) * 2011-04-25 2016-10-31 Юнилевер Нв Композиция для обработки твердой поверхности и способ ее использования
CN103540430A (zh) * 2012-07-10 2014-01-29 3M创新有限公司 空调散热器用清洗剂
JP5916562B2 (ja) * 2012-08-22 2016-05-11 株式会社クレハ フッ化ビニリデン系重合体の製造方法
DE102014012380A1 (de) * 2014-08-25 2016-02-25 Coin Consulting Ug (Haftungsbeschränkt) Vollwaschmitteltuch mit waschaktivem Substrat

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Publication number Priority date Publication date Assignee Title
DE4017667A1 (de) * 1990-06-01 1991-12-05 Henkel Kgaa Fluoridfreie reinigungsmittel fuer aluminiumoberflaechen
WO1994016045A1 (fr) * 1993-01-18 1994-07-21 Unilever N.V. Composition pour lave-vaisselle contenant un inhibiteur de corrosion
US6277805B1 (en) * 1993-11-22 2001-08-21 The Procter & Gamble Co. Alkaline liquid hard-surface cleaning composition containing a quaternary ammonium disinfectant and selected dicarboxylate sequestrants
US6069123A (en) * 1995-06-30 2000-05-30 Procter & Gamble Company Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety
EP1059378A1 (fr) * 1999-06-08 2000-12-13 The Procter & Gamble Company Lingette humide avec agent anti-mousse
EP1167510A1 (fr) * 2000-06-23 2002-01-02 The Procter & Gamble Company Lingette humide, jetable pour le nettoyage des surfaces dures
GB2370042A (en) * 2000-12-15 2002-06-19 Reckitt Benckiser Inc Hard surface cleaning compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8626216B2 (en) 2005-10-31 2014-01-07 Ntt Docomo, Inc. Transmission and reception bandwidth setting method, mobile terminal and base station in radio communication system that defines a plurality of signal bandwidths
US9185687B2 (en) 2005-10-31 2015-11-10 Ntt Docomo, Inc. Transmission and reception bandwidth setting method, mobile terminal and base station in radio communication system that defines a plurality of signal bandwidths

Also Published As

Publication number Publication date
DE602006008761D1 (de) 2009-10-08
AR053210A1 (es) 2007-04-25
CN101160384A (zh) 2008-04-09
AU2006233523B2 (en) 2010-06-03
ZA200708739B (en) 2009-08-26
ATE440937T1 (de) 2009-09-15
EP1869152A1 (fr) 2007-12-26
CA2602377A1 (fr) 2006-10-19
PL1869152T3 (pl) 2010-01-29
JP2008535981A (ja) 2008-09-04
BRPI0607911A2 (pt) 2009-11-03
RU2399655C2 (ru) 2010-09-20
RU2007141888A (ru) 2009-05-20
CN101160384B (zh) 2011-04-13
AU2006233523A1 (en) 2006-10-19
WO2006108475A1 (fr) 2006-10-19
CA2602377C (fr) 2013-09-24

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