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EP2920291B1 - Composition de nettoyage de surface - Google Patents

Composition de nettoyage de surface Download PDF

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Publication number
EP2920291B1
EP2920291B1 EP13773744.1A EP13773744A EP2920291B1 EP 2920291 B1 EP2920291 B1 EP 2920291B1 EP 13773744 A EP13773744 A EP 13773744A EP 2920291 B1 EP2920291 B1 EP 2920291B1
Authority
EP
European Patent Office
Prior art keywords
composition according
cleaning
granular
polymer
ash
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
Application number
EP13773744.1A
Other languages
German (de)
English (en)
Other versions
EP2920291A1 (fr
Inventor
Carlo Johannes van den BERGH
Neeraj Gupta
Paolo Mondani
Giovanni Taino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP13773744.1A priority Critical patent/EP2920291B1/fr
Publication of EP2920291A1 publication Critical patent/EP2920291A1/fr
Application granted granted Critical
Publication of EP2920291B1 publication Critical patent/EP2920291B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to granulated surface cleaning compositions, their manufacturing process and a method to clean surfaces using such compositions.
  • Abu rub comprises burnt waste or ash from plant material, such as the husk of rice.
  • the abu rub is rubbed onto cooking instruments which improves the detachment of food residue on the instrument surface. Thereafter the mixture of abu rub and food residue is removed, for example by scrapping, wiping with a cloth or a little water.
  • GB 1911/19,841 discloses a preparation for cleaning tin plates and the like.
  • the preparation comprises of a mixture of calcium sulphate and sawdust.
  • the preparation cleans grease and dirt from the surface of plates and leaves a brilliant finish. Further, the dust arising from the use of the composition in the cleaning machine is reduced considerably.
  • FR 2 881 142 A1 discloses a vegetal absorbing particles material used as cleaning agent wherein the vegetal absorbing material has an average particle size of from 0.350 to more than 0.700 mm.
  • a granular composition comprising a polyacrylic acid based swellable polymer, cellulose fiber and water.
  • the invention relates to a granular surface cleaning composition according to claim 1.
  • the granular composition according to the invention can be used to efficiently clean surfaces, with little or no use of added water.
  • the composition can optionally be mixed with ash to improve the surface cleaning efficiency of the ash, compared to the cleaning efficiency of the ash alone.
  • mixing said composition with a substantial amount of ash e.g. 50 wt. %) has little or no negative impact on the surface cleaning efficiency, compared to the cleaning efficiency of the granular composition alone.
  • the invention relates to a cleaning mixture comprising at least 25 wt. %, of the granular composition, according to any one of claims 1 to 12, and at most 75 wt. % of ash.
  • composition alone, or when admixed with ash, is suitable for cleaning surfaces in a method requiring little or no added water.
  • the invention relates to a surface cleaning method comprising the steps of:
  • the expressions "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 term 'soil' includes stubborn soil, which means strongly adhering soils that are typically very difficult to remove, such as burnt-on and/or baked-on food residues.
  • Weight percentage (wt. %) is based on the total weight of the composition unless otherwise stated.
  • the composition according to the invention is a granular composition, by which is indicated that it is powder-like.
  • home or place of work e.g. office
  • Home or place of work surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
  • Such hard surfaces may be found both in private households as well as in commercial, institutional and industrial environments.
  • Home or office hard surfaces include dish surfaces. With dish surfaces is meant herein dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene,polystyrene, etc.), wood, enamel, Inox, Teflon, or any other material commonly used in the making of articles used for eating and/or cooking.
  • An improved cleaning can be indicated by the removal of soil and/or stains from hard surfaces by a lower effort (e.g. less wiping actions, less force per wiping action or a combination thereof) necessary to reach a similar level of stain/soil removal. For example, less effort would be required to remove a certain amount of soil from a metal surface. Clearly, an improved cleaning (efficiency) may also be indicated by a similar effort to remove an increased amount of soil/stain.
  • the composition of the present invention comprises granules, wherein the average granular size is from 0.05 to 5 millimeter, preferably from 0.06 to 3, more preferably from 0.07 to 2 and even more preferably from 0.1 to 1 millimeter.
  • Said average granular sizes have several advantages. First of all it reduces the development of dust during the dry hand dishwashing. Secondly, the granular form promotes cleaning by physical abrasion of the cooking instruments. Thirdly, the granular form facilitates the optional mixing with the ash.
  • an average particle diameter is generally expressed as the d 3,2 value, which is the Sauter mean diameter, unless stated otherwise.
  • the Sauter mean diameter is the diameter of a sphere that has the same volume/surface area ratio as a particle of interest.
  • the diameter of the fiber as expressed herein is the diameter of a circle having the same surface area as the cross-section of the fiber.
  • the d 4,3 value which is the volume weighted mean diameter, may be used herein.
  • the volume based particle size equals the diameter of the sphere that has same the same volume as a given particle.
  • the composition according to the invention may comprise one or more composite granules, one or more single-component granules or any combination thereof.
  • the composition may comprise granules, wherein an individual granule comprises water swellable polymer, cellulose and water (i.e. composite granules).
  • the composition may comprise a mix of separately granulated swellable polymer, and cellulose (i.e. mix of single-component granules). It will be appreciated that water will typically be contained in granules and not form single component granules unless in extreme conditions, such as below freezing temperatures.
  • the individual granules according to the invention may have any suitable form to promote abrasive action.
  • the granules are irregular in size and shape and have sharp surface edges.
  • the granular cleaning composition according to the invention comprises polyacrylic acid based water swellable polymer.
  • polyacrylic acid based water swellable polymer is defined as polymers which are formed at least partially from acrylic acid monomers.
  • acrylic acid encompasses salt derivatives such as acrylate.
  • the molecular structure of polyacrylic acids may contain non-acrylic acid monomers, such as acrylamide monomers. Copolymers of acrylamide and polyacrylic acid are also encompassed by the term polyacrylic acid. However, preferably at least 40 wt. %, more preferably at least 60 wt. %, even more preferably 70 wt. % and still more preferably at least 90 wt.
  • % of the weight of the polymer is derived from acrylic acid monomers. It will be appreciated that with the 'weight of the polymer' is meant the molecular weight of the polymeric molecule, which does not include the weight of any non-covalently bound material such as absorbed water molecules.
  • the polymer according to the invention may comprise a homogeneous polyacrylic acid mixture comprised of one type of poylacrylic acid only.
  • the cleaning material may comprise a combination of poylacrylic acid types.
  • the polymer molecules of the polymer according to the invention may have the same or a varying chain length/ molecular weight.
  • the average molecular weight of the polyacrylic acids preferably is from 10, 000 to 50, 000, 000 Daltons, more preferably from 1, 000, 000 to 25, 000, 000 Daltons and even more preferably from 5, 000, 000 to 20, 000, 000 Daltons.
  • the polymers according to the invention may be (partially) cross-linked.
  • Cross-linking can be carried out by contacting the polymers with a suitable cross-linker, which is typically an organic molecule containing two or more double bounds.
  • suitable cross-linkers are tetraallylethoxy ethane, 1,1,1-trimethylolpropanetricrylate and N,N'-methylenebisacrylamide.
  • the polymer according to the invention is partially cross-linked and more preferably comprises 0.1 to 2 wt. %, even more preferably 0.2 to 1 wt. % and still even more preferably 0.3 to 0.8 wt. % of cross-linker, based on the total weight of the final polymer.
  • polymer 'comprising 0.5 wt. % of cross-linker' indicates that 0.5 wt. % of cross-linker was consumed in the process of cross-linking the polymer (i.e. and built into the polymer network).
  • cross-linker comprised by the polymer according to the invention is N,N'-methylene bisacrylamide.
  • Polymers according to the invention may be (partially) neutralized, which affects the charge density (ionicity) of the polymer.
  • Neutralization can be carried out by contacting the polymer with a neutralizing agent, such as sodium carbonate or sodium hydroxide.
  • the polymers according to the invention are partially cross-linked and partially neutralized.
  • the polymer according to the invention has a five-minute absorbency under load (AUL) of at least 10 g/g, more preferably of at least 15 g/g, even more preferably of at least 18 g/g, still even more preferably of at least 21 g/g.
  • AUL absorbency under load
  • the five-minute absorbency under load is determined according to the method described in US 5,149,335 which is hereby incorporated by reference.
  • Polyacrylic acids which may be used in the cleaning composition according to the invention are commercially available.
  • Aquasorb 3005 SNF FLOERGER
  • Stockosorb, FAVOR EONIK industries
  • Water Lock A-180', A- 220, B-204, G-404, G-504, G-580 Ginning Processing
  • Acusol 771, 772 Rohm & Haas
  • Luquasorb 1280, L74 SAP BASF
  • ADM Lysac ActyFill 20
  • 432776, 436364, 435325 Sigma Aldrich
  • Petrolsorb Watersorb
  • Disintex 200 ISP
  • the granular surface cleaning composition according to the invention comprises from 0.2 to 12 wt. % of polyacrylic based swellable polymer, preferably from 0.5 to 8 wt. % and even more preferably from 1 to 5 wt. %.
  • the cellulose fibers (the terms 'cellulose fiber' and 'cellulose fibers' are used interchangeably) according to the invention can be plant-derived.
  • Cellulose fibers are believed to principally consist of linear chains of Beta-linked D-glucose units.
  • Common sources of cellulose fibers are cotton, bamboo silk, milled corn cobs or wood pulp (e.g. saw dust).
  • Wood pulp is typically derived from softwood trees such as spruce, pine, fir, larch, hemlock or hardwoods such as eucalyptus, aspen and birch and in particular is typically made from the heartwood and the sapwood (e.g. and typically not from the bark).
  • the process to manufacture pulp is known to the person skilled in the art and may involve mechanical, semi-mechanical and/or fully chemical methods.
  • the manufacturing procedure of the plant pulp may influence the amount of lignin and hemicelluloses in the plant pulp.
  • the pulp may be bleached or non-bleached.
  • the cellulose fiber according to the invention has an average fiber length of from 10 to 5,000 micron ( ⁇ m), more preferably from 25 to 2,500 micron and even more preferably from 50 to 500 micron.
  • the cellulose fiber according to the invention has an average fiber thickness of from 2 to 200 micron ( ⁇ m), more preferably from 5 to 100 micron and even more preferably 10 to 50 micron.
  • the granular surface cleaning composition according to the invention comprises from 10 to 80 wt. % of cellulose fiber, preferably from 20 to 75 wt. %, more preferably from 30 to 70 wt. %, even more preferably from 40 to 65 wt. %.
  • the cellulose fiber according to the invention have an oil absorbing capacity of at least 5 w/w, more preferably of at least 7 w/w, even more preferably of at least 10 w/w, still even more preferably of at least 15 w/w and still even more preferably of at least 20 w/w.
  • the cellulose fibers according to the invention are natural cellulose fibers (e.g. have not been subjected to chemical modification and more specifically is not carboxymethyl cellulose).
  • the oil absorbing capacity is measured according to the following method, which is based on 'the Standard Test Method for Oil Absorption of Pigments by Spatula Rub-out' (ASTM international, test number D281-12):
  • One gram of cellulose fiber is weighed and placed upon a glass plate.
  • a bottle of with a known weight-amount of linseed oil is provided and used to add oil to the fiber, drop by drop. After the addition of each drop, the oil is thoroughly incorporated by rubbing up with a spatula. The addition of linseed oil is continued until a very stiff, putty-like paste, that does not break or separate is formed.
  • the weight of added oil is determined (e.g. by weighing the amount of oil added from the bottle of linseed oil) and thereby amount of oil absorbed by the fiber w/w (e.g. gram of oil absorbed per gram of fiber) determined.
  • Cellulose fibers according to the invention are commercially available, for example under the trade name 'ARBOCEL Grade B 800', 'ARBOCEL Grade BE 600-20' (J. RETTENMAIER & S ⁇ HNE GMBH, Holzmeuhle 1, Rosenberg, Germany); 'Oil Sponge AB' (PHASE III, 315 E Warner Rd, Chandler Arizona, USA); 'Bamboosilk' (Soliance, Place de la Madeleine 30, Paris, France); 'PowderSorb' (Applied Science & Advanced Technologies, Inc (ASAT, Inc), 10636 Linkwood CourtBaton Rouge, LA 70810,USA; and 'OILSPONGE Absorbents' (PHASEIII Chandler, AZ 85225 USA).
  • the granular surface cleaning composition according to the invention comprises water which reduces dustiness and improves granule size stability.
  • the composition according to the invention comprises from 10 to 45 wt. %, preferably from 20 to 40 wt. % and even more preferably from 25 to 35 wt. % of water. It will be appreciated that the water is typically completely comprised by the granules.
  • the granular surface cleaning composition according to the invention may comprise additional ingredients.
  • Optionally added ingredients which are solid can be comprised by composite granules or form (single-component) granules themselves.
  • optionally added ingredients are liquids it will be appreciated these will typically be part of (e.g. absorbed) composite granules and that the composition will preferably remain a free flowing powder and preferably without any visible liquid (e.g. water, oil).
  • the granular cleaning composition according to the invention comprises surfactant.
  • Said surfactant (detergent active) is generally chosen from anionic and nonionic detergent actives.
  • the cleaning composition may further or alternatively comprise cationic, amphoteric and zwitterionic surfactants.
  • Said granular cleaning composition comprises from 0.1 to 30 wt. %, more preferably from 0.5 to 15 wt. %, even more preferably from 1 to 10 wt. % and still even more preferably from 2 to 7 wt. % of surfactant.
  • a suitable surfactant is conventional soap (i.e. salt of fatty acids, such as sodium stearate).
  • 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, alkylnaphthalene-sulphon
  • the amount present in the granular cleaning composition of the invention will generally be at least 0.1 wt. %, preferably at least 0.5 wt. %, more preferably at least 1.0 wt. %, but not more than 20 wt. %, preferably at most 10 wt. % and more preferably not more than 5 wt. %.
  • 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:
  • nonionic surfactants are:
  • the amount present in the granular cleaning composition of the invention will generally be at least 0.1 wt. %, preferably at least 0.5 wt. %, more preferably at least 1.0 wt. %, but not more than 20 wt. %, preferably at most 10 wt. % and more preferably not more than 5 wt. %.
  • amphoteric, cationic or zwitterionic surfactants in the granular cleaning composition 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 chloride.
  • 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 C12-C16 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 from coconut oil
  • 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 .
  • the granular surface cleaning composition according to the invention comprises from 1 to 50 wt. %, more preferably from 2 to 40 wt. %, even more preferably from 3 to 30 wt. %, still even more preferably from 4 to 25 wt. % and still even more preferably from 5 to 15 wt. % of abrasive particles.
  • abrasive particles may depend on the intended use and in particular the sensitivity of the surface to scratching.
  • a granular cleaning composition according to the invention which is intended for use as dry dish washing comprises abrasive particles.
  • the abrasive particles can be of any suitable material, both organic and inorganic.
  • inorganic abrasive particles are abrasive particles made of zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates and sulphates.
  • the abrasive particles have sharp edges and an average a particle has at least one edge or surface having concave curvature. More preferably, the particles herein have a multitude of sharp edges and each particle has at least one edge or surface having concave curvature.
  • the sharp edges of the particles are defined by edges having a tip radius below 20 pm, preferably below 8 pm, most preferably below 5 pm.
  • the tip radius is defined by the diameter of an imaginary circle fitting the curvature of the edge extremity.
  • the average size of the abrasive particles is 1 to 200 ⁇ m, more preferably is 2 to 150 ⁇ m, even more preferably is at most is 3 to 100 ⁇ m and still even more preferably is 5 to 50 ⁇ m. It will be appreciated that abrasive particles may be comprised as single component and/or as composite granules and that the average granule size according to the invention (e.g. not below 0.05 milimeter) is adhered to.
  • Abrasive calcite particles in a range of different average particles sizes are commercially available.
  • calcite particles with a mean particle size of 2.6, 5 or 35 ⁇ m are available for example under trade names Omyacarb 2 - AV, Omyacarb 5 - AV and Omyacarb 30 - AV respectively (Omya Greater South, Milano, Italy).
  • organic abrasive particles are abrasive particles made from nut shells (e.g. walnut shells) or olive stones.
  • the granular surface cleaning composition according to the invention comprises abrasive calcite particles.
  • the composition according to the invention may contain other ingredients, such as, colorants, whiteners, preservatives and aroma compounds.
  • the granular cleaning composition according to the invention has a color which is different from ash, the color of ash typically being grey to black. This is believed to aid in visually assessing the degrees of mixing of the ash with the granular composition of the invention.
  • the granular composition according to any one of claims 1 to 12 can be mixed with ash before use as surface cleaning agent.
  • the ash as used herein is defined as the residue left after the burning of organic material, which preferably is plant material and more preferably is wood. It will be appreciated that the terms ash encompasses the material typically found in home-style wood stoves/ hearths after the burning of wood. Calcium carbonate is believed to be a principal component of the ash derived from of organic material, which typically further comprises potash, phosphate and other mineral elements.
  • the granular composition according to the invention has a cleaning efficiency, which is superior to that of only ash. It was observed that mixing up to 50 wt. % of wood ash with 50 wt. % of the granular composition had little or no negative effect on the cleaning efficiency (compared to the cleaning efficiency of the granular composition alone (i.e. unmixed with ash)). Also the cleaning efficiency of a mixture of 50 wt. % of ash with 50 wt. % of the granular composition according to any one of claims 1 to 12 was found to be far superior with that of only ash.
  • the invention relates to a cleaning mixture comprising at least 25 wt. % of the granular composition according to any one of claims 1 to 12, and 0.5 to 75 wt. % of ash.
  • said cleaning mixture comprises at least 40 wt. %, more preferably at least 50 wt. %, even more preferably at least 60 wt. % and still even more preferably at least 75 wt. % of the granular composition according to any one of claims 1 to 12.
  • said cleaning mixture comprises 1 to 60 wt. %, more preferably 5 to 50 wt. %, even more preferably 10 to 40 wt. % and still even more preferably 15 to 25 wt. % of ash.
  • the cleaning mixture may comprises additional components but will mainly consist of ash and the granular composition.
  • at least 50 wt. %, more preferably at least 75 wt. % and even more preferably at least 95 wt. % of the weight of the cleaning mixture is derived from the combined weight of the polyacrylic acid based swellable polymer, cellulose fiber, water and the ash.
  • the composition according to the invention can be made by simply mixing the (liquid and solid components).
  • the average granule size can be manipulated by the amount of liquid components added.
  • the granule size can modified using techniques known it the art. For example pelleting can be used to increase granule size. For example, milling and grinding can be used to decrease granule size. For example sieving can be used to measure and/or select granules of a certain average size.
  • composition according to the invention is granular and preferably will not contain any visible free liquid (e.g. water, oil).
  • the granular cleaning composition according to the invention can be used to clean surfaces by itself or optionally as mixed with ash without the use of added water.
  • the granular nature allows easy mixing with the ash, which can be achieved by any suitable means, such as simply by hand.
  • composition according to the invention improved the cleaning capability of ash on hard surfaces. Therefore the granular composition (with or without ash) is particularly useful for to clean dishes and/or hard floors requiring little or no added water (e.g. waterless dish washing).
  • Cleaning may be carried out by simply applying the surface cleaning composition by itself, or mixed with ash, to the surface to be cleaned and leaving it stand for a sufficient period of time. It will be appreciated that to remove or reduce a specific stain/soil from a surface, the granular composition should be applied to said stain/soil
  • the applied composition is agitated on the surface.
  • the agitation may be manual, such as by the act of rubbing and/or swiping.
  • the agitation may also be carried out using suitable mechanical devices known in the art, such as a brush.
  • the applied composition and the optionally applied ash can be removed from the surface, preferably without the aid of added water.
  • the waterless removal may be done by any suitable means such as by use of a brush, a vacuum cleaner, air movement or in some cases even gravity. It will be appreciated that depending on the type of stain/soil, some means will be more suitable than other to remove the applied material. For example, liquid stains/soils will readily be absorbed and possible coagulate the granules into a paste. In such a case, brushing is more suitable for removal than the use of air movement.
  • the invention relates to a surface cleaning method comprising the steps of:
  • the removing of the applied material at step 'c' is performed by brushing.
  • dish surfaces is meant herein dishes, glasses, pots, pans, baking dishes and flatware made from ceramic, china, metal, glass, plastic (polyethylene, polypropylene,polystyrene, etc.), wood, enamel, Inox, Teflon, or any other material commonly used in the making of articles used for eating and/or cooking.
  • the method according to the invention is used to clean floor surfaces (e.g. tiles or carpet), more preferably hard floor surfaces with little or no added water.
  • floor surfaces e.g. tiles or carpet
  • the cleaning efficiency was assessed by measuring stain removal from a white ceramic tile using a gravimetric assay according to the following steps:
  • the stain removal i.e. cleaning efficiency
  • the stain removal was determined by subtracting the final weight measured at step '4' from the initial weight of the tile measured at step '1'. A lower increase in weight is indicative of an improved cleaning efficiency.
  • the cleaning efficiency was quantified as the amount of wt. % of stain, which was removed from the tile, based on the initial stain weight of 1gram. Experiments were carried out in triplicate.
  • Example 1 and Comparative A were prepared according to the formulation as indicated in table 1. Table 1. Formulation of Example 1 and Comparative A. Wt. % Ingredients Example 1 Example 2 Comparative A Cellulose fibers B800 1 60 30 - Perfume 0.1 0.05 - Partially cross-linked polyacrylic acid 2 3 1.5 - CocoAmine Oxide 2 1.0 - Burnt wood ash 3 - 50 100 Water to balance to balance 1.Tradename: ARBOCEL Grade B 800, Supplier: J. RETTENMAIER & S ⁇ HNE GMBH 2. Tradename: Polyhipe, Supplier: Rohm and Haas Company. 3. The burnt wood ash was obtained from a home hearth which was used to burn wood.
  • Example 1 The components of Example 1 were mixed and a granular composition with an average granule size of about 0.3 mm was obtained.
  • Example 2 was made by mixing 50 wt. % of burnt wood ash with 50 wt. % of the granular composition of Example 1.
  • Example 2 The cleaning efficiency of Example 1, Example 2 and Comparative 1were assessed using the gravimetric assay as described (Table 2).
  • the staining material was either stain-type 'a' (liquid vegetable oil comprising 0.002 wt. % of Sudan Red as coloring) or stain-type 'b' (a 1:1weight mixture of liquid vegetable oil and water further comprising 0.002 wt. % Sudan Red). Table 2. Cleaning efficiency wt.% of stain removed Stain-type a Stain-type b Example 1 72 81 Example 2 67 81 Comparative A 27 28

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

Claims (14)

  1. Composition nettoyante de surface granulaire comprenant :
    • de 0,2 à 12 % en masse de polymère gonflable à base de poly(acide acrylique) ;
    • de 10 à 80 % en masse de fibre de cellulose ;
    • de 10 à 45 % en masse d'eau ;
    • de 0,1 à 30 % en masse de tensioactif ;
    • de 1 à 50 % en masse de particules abrasives ;
    où la taille moyenne de granulé est de 0,05 à 5 millimètres.
  2. Composition selon la revendication 1, où la taille moyenne granulaire est de 0,06 à 3, encore mieux de 0,07 à 2 et bien mieux encore de 0,1 à 1 millimètre.
  3. Composition selon la revendication 1 ou la revendication 2, où la masse moléculaire moyenne du polymère est de 10 000 à 50 000 000 Daltons, de préférence de 1 000 000 à 25 000 000 Daltons et encore mieux de 5 000 000 à 20 000 000 Daltons.
  4. Composition selon l'une quelconque des revendications 1 à 3, où le polymère est partiellement réticulé et comprend encore mieux de 0,1 à 2 % en masse, bien mieux encore de 0,2 à 1 % en masse et particulièrement de préférence de 0,3 à 0,8 % en masse de réticulant, sur la base de la masse totale du polymère final.
  5. Composition selon l'une quelconque des revendications 1 à 4, où au moins 70 % en masse, de préférence au moins 80 % en masse, encore mieux 90 % en masse et particulièrement de préférence au moins 95 % en masse de la masse du polymère sont dérivés de monomères d'acide acrylique.
  6. Composition selon l'une quelconque des revendications 1 à 5, où une quantité de polymère est de 0,5 à 8 % en masse, de préférence de 1 à 5 % en masse.
  7. Composition selon l'une quelconque des revendications 1 à 6, où une quantité de fibre de cellulose est de 20 à 75 % en masse, de préférence de 30 à 70 % en masse et encore mieux de 40 à 65 % en masse.
  8. Composition selon l'une quelconque des revendications 1 à 7, où les fibres de cellulose présentent une capacité d'absorption d'huile d'au moins 5 masse/masse, encore mieux d'au moins 7 masse/masse, bien mieux encore d'au moins 10 masse/masse, particulièrement de préférence d'au moins 15 masse/masse et particulièrement encore mieux d'au moins 20 masse/masse.
  9. Composition selon l'une quelconque des revendications 1 à 8, où la quantité d'eau est de 20 à 40 % en masse et de préférence de 25 à 35 % en masse.
  10. Composition selon l'une quelconque des revendications 1 à 9, comprenant de 0,5 à 15 % en masse, encore mieux de 1 à 10 % en masse et bien mieux encore de 2 à 7 % en masse de tensioactif.
  11. Composition selon l'une quelconque des revendications 1 à 10, comprenant de 1 à 50 % en masse, de préférence de 2 à 40 % en masse, encore mieux de 3 à 30 % en masse, bien mieux encore de 4 à 25 % en masse et particulièrement de préférence de 5 à 15 % en masse de particules de calcite abrasive.
  12. Mélange nettoyant comprenant au moins 25 % en masse de la composition granulaire selon l'une quelconque des revendications 1 à 11 ; et de 0,5 à 75 % en masse de cendre.
  13. Procédé pour le nettoyage d'une surface comprenant les étapes de :
    a) application de la composition granulaire selon l'une quelconque des revendications 1 à 11 ; et éventuellement de cendre à une surface ;
    b) éventuellement agitation des granulés sur la surface ;
    c) élimination du matériau appliqué dans l'étape « a », de préférence sans utiliser d'eau ajoutée, comme par brossage.
  14. Procédé selon la revendication 13, où la surface est une surface de plat ou de sol et de préférence une surface de sol dur.
EP13773744.1A 2012-11-16 2013-10-07 Composition de nettoyage de surface Not-in-force EP2920291B1 (fr)

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EP12192944 2012-11-16
EP13773744.1A EP2920291B1 (fr) 2012-11-16 2013-10-07 Composition de nettoyage de surface
PCT/EP2013/070789 WO2014075845A1 (fr) 2012-11-16 2013-10-07 Composition de nettoyage de surface

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EP2920291A1 EP2920291A1 (fr) 2015-09-23
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CN (1) CN104822819A (fr)
BR (1) BR112015009996A2 (fr)
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WO (1) WO2014075845A1 (fr)
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EP3174967B1 (fr) * 2014-08-01 2018-06-13 Unilever N.V. Composition de nettoyage d'une surface dure
DE102015107637B4 (de) * 2015-05-15 2024-06-20 Alfred Kärcher SE & Co. KG Pulverförmiges Reinigungsmittel
EP3519549A4 (fr) * 2016-09-30 2020-06-03 Novaflux, Inc. Compositions de nettoyage et de décontamination
DE102017002129A1 (de) * 2017-03-08 2018-09-13 Carl Freudenberg Kg Reinigungsartikel
WO2019195403A1 (fr) 2018-04-03 2019-10-10 Novaflux, Inc. Composition de nettoyage ayant un polymère superabsorbant
CA3156824A1 (fr) 2019-10-03 2021-04-08 Novaflux Inc. Composition, procede et appareil de nettoyage de cavite buccale
US12064495B2 (en) 2019-10-03 2024-08-20 Protegera, Inc. Oral cavity cleaning composition, method, and apparatus

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Publication number Priority date Publication date Assignee Title
GB191119841A (en) 1911-09-06 1912-07-11 Charles Gibbons Improved Preparation for Cleaning Tin PLates and the like.
US1990067A (en) * 1931-03-20 1935-02-05 Walter S Finken Fluid clutch and transmission
DE3927975A1 (de) * 1989-04-13 1990-10-18 Vorwerk Co Interholding Pulverfoermiges reinigungsmittel
US5149335A (en) 1990-02-23 1992-09-22 Kimberly-Clark Corporation Absorbent structure
RO110958B1 (ro) * 1991-03-11 1996-05-30 Institutul Politehnic Praf de curățat
RU2093549C1 (ru) * 1992-12-01 1997-10-20 Хабаровский филиал Дальневосточного научно-исследовательского института гидротехники и мелиорации Чистящее средство для предметов домашнего обихода
US5990067A (en) * 1997-12-05 1999-11-23 Franssen; Todd Concrete surface cleaning composition and method
DE59900108D1 (de) * 1999-03-29 2001-07-05 Dalli Werke Waesche & Koerperp Sprengmittelgranulat enthaltende Waschmitteltabletten
CN1300812A (zh) * 1999-12-22 2001-06-27 普罗格特-甘布尔公司 擦洗组合物
AU2002247932A1 (en) * 2002-03-26 2003-10-08 Council Of Scientific And Industrial Research Scouring powder composition and process of production thereof
PL202080B1 (pl) * 2002-11-15 2009-05-29 Unilever Nv Synergistyczna detergentowa kompozycja
FR2874618B1 (fr) * 2004-08-27 2007-09-07 Philippe Morin Super degraissant
FR2881142A1 (fr) * 2005-01-26 2006-07-28 Cbs Ingredients Sarl Absorbant vegetal

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EA027538B1 (ru) 2017-08-31
TR201802780T4 (tr) 2018-03-21
BR112015009996A2 (pt) 2017-07-11
EP2920291A1 (fr) 2015-09-23
ZA201503399B (en) 2016-11-30
WO2014075845A1 (fr) 2014-05-22
CN104822819A (zh) 2015-08-05
EA201500542A1 (ru) 2015-09-30

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