EP1670890A1 - Procede de nettoyage - Google Patents

Procede de nettoyage

Info

Publication number
EP1670890A1
EP1670890A1 EP04768525A EP04768525A EP1670890A1 EP 1670890 A1 EP1670890 A1 EP 1670890A1 EP 04768525 A EP04768525 A EP 04768525A EP 04768525 A EP04768525 A EP 04768525A EP 1670890 A1 EP1670890 A1 EP 1670890A1
Authority
EP
European Patent Office
Prior art keywords
foam
acid
cleaning
fabric
water
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.)
Granted
Application number
EP04768525A
Other languages
German (de)
English (en)
Other versions
EP1670890B1 (fr
Inventor
Mattia De Dominicis
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.)
Reckitt Benckiser NV
Original Assignee
Reckitt Benckiser 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
Priority claimed from GB0323394A external-priority patent/GB0323394D0/en
Priority claimed from GB0409178A external-priority patent/GB2413336A/en
Application filed by Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Publication of EP1670890A1 publication Critical patent/EP1670890A1/fr
Application granted granted Critical
Publication of EP1670890B1 publication Critical patent/EP1670890B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0094High foaming compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40Specific cleaning or washing processes
    • C11D2111/42Application of foam or a temporary coating on the surface to be cleaned

Definitions

  • the invention relates to method of treating soft surfaces by the production of a stable foam from a solution of a cleaning formulation and applying the stable foam to the fabric, the invention includes the cleaning formulation itself comprising a source of hydrogen peroxide, such as sodium percarbonate, and at least one surfactant .
  • the invention includes a device for a preparation of the stable foam.
  • the stable foam can be used for direct treatment of stains on soft surfaces (fabric or carpet) and it is prepared by mixing a solution of a cleaning formulation, preferably in combination with aerating, for, preferably, less than 5, 4, 3, 2 minutes: preferably the foam is formed quickly, in less than 1 minute, between 5 and 50, 10 and 40 seconds from mixing with water.
  • the cleaning formulation is a solid, such as a granular, compacted or powder composition, ideally the cleaning formulation is granular or powder, to aid dissolution in water.
  • warm water is used (greater than 25, 30, 40 or 50°C, ideally less than 80, 70, 60, 50°C) .
  • a method of cleaning stains on a soft surface comprising mixing (preferably dissolving) a solid, preferably a powder, cleaning formulation in water, the formulation comprising a source of active oxygen and at least one surfactant with water to form a stable foam and applying the foam directly onto the stained soft surface.
  • a further feature of the invention includes a device for the aeration of aqueous surfactant mixtures comprising a cellular plastic attached to a rigid support surface the opposition face of the rigid support surface being attached to a handle.
  • a further feature of the invention includes a kit for treating stain on soft surfaces comprising a solid, preferably a powder, stain cleaning composition comprising a source of active oxygen and at least one surfactant and a device for the mixing/ aerating of the cleaning composition to form a stable foam for application onto the stain.
  • a kit for treating stain on soft surfaces comprising a solid, preferably a powder, stain cleaning composition comprising a source of active oxygen and at least one surfactant and a device for the mixing/ aerating of the cleaning composition to form a stable foam for application onto the stain.
  • Further optional subsequent steps include one or more of the following; a) rubbing the stained soft surface; b) cleaning the fabric in a fabric washing machine, with or without the addition of a fabric detergent; c) rinsing with water the stable foam formulation from the soft surface.
  • the time period between applying the stable foam and any of the subsequent steps is at least 10, 20, 30, 40, 50, 60 seconds, ideally more than 1 , 2 , or 3 minutes, advisably the stable foam is not left for more than 10, 9, 8, 7, 6, 5, or 4 minutes.
  • stable we mean that the foam retains at least 80%, 90% or 95% of its volume for 2 minutes after its formation.
  • the foam is prepared by dissolving 15 grams of solid composition into 100 ml of water at 40°C.
  • the stable foam may be prepared by any suitable mixing device or aeration device to incorporate air into the cleaning formulation solution.
  • the ?????? device offers particular advantages in ensuring that all of the solid composition is dissolved prior to application.
  • a cleaning solution containing a foaming surfactant is necessary for preparing the stable foam.
  • the inclusion of the cleaning formulation of a source of active oxygen provides for oxygen to be evolved during dissolution further providing a rapid development of the stable foam.
  • a container is also ideally required where the stable foam is prepared.
  • the stable foam is prepared by the use of cellular plastic.
  • Cellular plastics are those with a density of between 1 and 500 kg/m 3 preferably between 20 and 80 kg/m 3 and with an average pore diameter of at least 0.1 mm, preferably at least 0.4 mm.
  • the cellular plastic has a porosity of >50%, >60%, >70% or >80%.
  • the "porosity" according to the embodiment is obtained by measuring with a dry automatic densimeter an apparent volume and a true volume of the cellular pastic material, and calculated in accordance with the following equation.
  • Porosity % (apparent volume-true volume) /apparent volumexlOO
  • the "average pore diameter” is a value measured in accordance with ASTM (Designation: D4404-84) and is specifically a value determined by the measurement of the diameter of pores in accordance with a mercury penetration process using a mercury porosimeter manufactured by Porous Material , Inc .
  • Suitable cellular plastics are those readily available for example from Euro foam, Miarka and Menshen and are made by any table water-insoluble plastic such as cellulose, polyurethane, polyester, polyether, or blends thereof .
  • the cellular plastic is attached to a handle so that the user does not need to get their hands wet.
  • the device comprising the cellular plastic is plunged into the cleaning formulation containing solution and pressed several times such that the liquid is aerated to form the stable foam when the formulation is squeezed through the cellular plastic.
  • the device can be moved up and down pushing it against the bottom of a suitable container, until the cleaning formulation is transformed into the stable foam.
  • the time necessary to create the foam with a suitable cellular plastic is quite low, between 10 and 60 seconds, typically below 2 minutes.
  • the solution is pumped by each up and down movement through the pores of the cellular plastic to form the stable foam.
  • the liquid excess can be squeezed out from the cellular plastic component.
  • the cellular plastic can be then dipped into the foam and applied onto the surface to be treated.
  • the device can also be used to rub the surface with the cellular plastic component. During the rubbing action the cleaning foam can more easily penetrate the stain that can in addition be adsorbed by the cellular plastic.
  • a rinsing step might be necessary or eventually in the case of fabric, a normal wash can be done in a fabric washing machine .
  • the device consists of at least two components, a handle 2 and cellular plastic 1, attached to the handle by a glue or a heat seal .
  • the handle (1) can be formed for example by one piece or two identical stick parts attached together through a screwing system. Each stick has a diameter from 1 mm to 6 cm, preferably from 3 mm to 12 mm and it may have a cavity running through the centre to reduce weight and material costs.
  • the wall thickness of the handle (1) is from 0.1 mm up to 1 mm, preferably between 0.1 mm to 0.5 mm.
  • the handle length may range from 1 cm up to 25 cm, preferably from 3 cm to 15 cm.
  • the handle can be made of wood, metal or plastic.
  • a plastic material and more preferred plastic materials are polyethylene, polypropylene, polystyrene, or PET.
  • the handle is attached to a support (2) that is a disk with a diameter from 1 cm to 30 cm, preferably from 3 cm to 10 cm. The thickness can range from 0.1 mm up to 12 cm, preferably from 0.5 to 10 mm.
  • the support (2) can be made of wood, metal or plastic.
  • plastic material and more preferred are polyethylene, polypropylene, polystyrene, or PET.
  • the cellular plastic (3) can be any shape but is preferably cylindrical shape.
  • the diameter can range from 1 cm to 20 cm, preferably from 3 cm to 10 cm.
  • the height can range from 0.1 mm up to 50 mm, preferably from 1 to 10 mm.
  • the cellular plastic can be made of synthetic materials as polyurethane, polyester, polyether, or a blend thereof or natural cellulose.
  • the support (2) can be attached to the handle (1) by heat sealing, with a glue or with any screw system type.
  • the cellular plastic (3) is attached to the support (2) by heat sealing or with a glue.
  • the cleaning formulation contains oleoyl sarcosinate (preferably as a sodium salt) , a source of active oxygen, such as sodium percarbonate, and pre erably at least one other surf ctant .
  • oleoyl sarcosinate preferably as a sodium salt
  • a source of active oxygen such as sodium percarbonate
  • oleoyl sarcosinate especially where the composition is applied directly onto the stain.
  • the above surfactant types can be used in combination with other surfactants, such as alcohol ethoxylates and alkyl sulphates .
  • a combination of alkyl naphthalene sulfonates and oleoyl sarcosinates provide improved stain removal efficacy for laundry detergent products .
  • the alkyl naphthalene sulfonates and oleoyl sarcosinate surfactant combination of the present invention can be also used in combination with a source of active oxygen, such as sodium percarbonate, and bleach activators, such as TAED.
  • Other ingredients that can be used include polymers, chelating agents, fillers, solvents, enzymes, fragrances and other minor components such as preservatives, dyes, thickeners and antifoaming agents.
  • Actives present in the detergent formulations of this invention include an one or more of the following: a) Anionic and/or nonionic surfactant, preferably an oleoyl sarcosinate and/or an alkyl naphthalene sulfonate and/or an alkyl sulphate each at an overall level of 0.1 to 30%wt, preferably 0.5 to 20%wt, and ideally 1 to l0%wt. b) Source of active oxygen, such as sodium percarbonate, preferably at a range of 0.1 to 80%wt, preferably from 10 to 70%wt, and ideally 30 to 60%wt.
  • Anionic and/or nonionic surfactant preferably an oleoyl sarcosinate and/or an alkyl naphthalene sulfonate and/or an alkyl sulphate each at an overall level of 0.1 to 30%wt, preferably 0.5 to 20%wt, and ideally 1 to l0%wt.
  • Builder such as polymers or chelating agents, preferably at a range of 0.1 to 80%wt, preferably from 1 to 60%wt, and ideally from 10 to 50%wt.
  • Bleach activator such as TAED, preferably at a level of 0.1 to 8%wt, preferably from 0.2 to 7%wt.
  • Superwetting agent preferably at a level from 0.01 to 10%wt.
  • Filler such as sodium sulfate, preferably to 100% formula composition.
  • the soft surface is a fabric, ideally clothing.
  • the composition is particularly effective on coloured fabric, especially cotton, providing for ? colour sa e bleaching composition.
  • Alkyl sulphate surfactants for use herein are those according to the formula R 2 S0M wherein R 2 represents a saturated or unsaturated alkyl group containing from 9 to 30 carbon atoms, preferably from 9 to 18 carbon atoms, more preferably from 9 to 14, even more preferably from 9 to 12 and most preferably 10.
  • the alkyl group can be in straight or branched configuration, and preferably in straight configuration.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium) or ammonium or substituted ammonium cations.
  • substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof.
  • Suitable examples are sodium, potassium, ammonium nonyl sulphate, decyl sulphate, dodecyl sulphate and/or octyl decyl sulphate.
  • sodium decyl sulphate is commercially available from ALLBRIGHT & WILLSON under the name EMPICOL 0137 ® .
  • Alkyl naphthalene sulfonate anionic surfactants are described in the formula below:
  • R is a straight chain or branched alkyl chain having from about 1 to about 25 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average
  • M is a cation capable of washing the compound more water soluble than the free acid especially preferred is an alkali metal (such as sodium or magnesium) , or ammonium or substituted ammonium preferred cation.
  • Oleoyl sarcosinates are described below: O I I R- CH 2 CH 2 -C -NH(R 1 )CH 2 -C -00 M I I o
  • R and R 1 is a straight chain or branched alkyl chain having from 1 to about 30 carbon atoms, saturated or unsaturated, and the longest average linear portion of the alkyl chain is 15 carbon atoms or less
  • M is a cation capable of making the compound more water soluble especially than the free acid, especially preferred is an alkali metal (such as sodium, potassium or magnesium) , or ammonium or substituted ammonium cation
  • NRx and x is from 0 to about 4.
  • Preferred total level of surfactant is in the range from 0.01 to 50% wt, ideally 0.1 to 30% wt and preferably 0.5 to 10% w . Additional nonionic and anionic surfactants can be used.
  • the nonionic surfactant is preferably a surfactant having a formula RO (CH2CH20) nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12.
  • R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12.
  • examples of other non-ionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide.
  • nonionic surfactants include primary alcohol ethoxylates (available under the Neodol tradename from Shell Co.), such as Cll alkanol condensed with 9 moles of ethylene oxide (Neodol 1-9) , C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-13 alkanol with 9 moles of ethylene oxide (Neodol 23-9) , C12-15 alkanol condensed with 7 or 3 moles ethylene oxide (Neodol 25-7 or Neodol 25-3) , C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), C9-11 linear ethoxylated alcohol, averaging 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91- 2.5), and the like.
  • Neodol tradename available under the Neodol tradename from Shell Co.
  • nonionic surfactants suitable for use in the present invention include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • examples of commercially available non-ionic detergents of the foregoing type are Cll-15 secondary alkanol condensed with either 9 moles of ethylene oxide (Tergitol 15-S-9) or 12 moles of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical .
  • Octylphenoxy polyethoxyethanol type nonionic surfactants for example, Triton X-100, as well as amine oxides can also be used as a nonionic surfactant in the present invention.
  • linear primary alcohol ethoxylates are available under the Tomadol tradename such as, for example, Tomadol 1-7, a Cll linear primary alcohol ethoxylate with 7 moles EO; Tomadol 25-7, a C12-C15 linear primary alcohol ethoxylate with 7 moles EO;
  • Tomadol 45-7 a C14-C15 linear primary alcohol ethoxylate with 7 moles EO; and Tomadol 91-6, a C9-C11 linear alcohol ethoxylate with 6 moles EO.
  • Other nonionic surfactants are amine oxides, alkyl amide oxide surfactants.
  • Preferred anionic surfactants are frequently provided as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts.
  • sulfate or sulfonate compounds including: alkyl benzene sulfates, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarcosinates, acyl isethionates, and N-acyl taurates
  • a super wetting agent is capable of reducing the surface tension in water at values below 25 mN/m, in the range between 18 and 25 mN/m at concentrations of 0.0001-l%wt, preferably between 0.001 and 0.1%wt.
  • Preferred levels in the cleaning composition are between 0.01 and 10%wt.
  • super wetting agents of this invention are silicone glycol copolymers and flurosurfactants.
  • the silicone glycol copolymers are described by the following formula:
  • X, Y, m and n are each a whole number ranging from 0 to 25, provided that X or Y is at least 1.
  • X is between 0-10 and y, m and n are each preferably between 0-5.
  • R and R' are straight chain or branched alkyl chain having from about 1 to about 25 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average.
  • the fluorinated surfactant is described in the following formulae : F(CF 2 ) n -CH 2 CH 2 -S-CH 2 CH 2 -COOM
  • n, m and x are integers having a value from 0 to 15; preferred values are between 1 and 12.
  • M is a cation which makes the compound water soluble especially an alkali metal such as sodium or magnesium, ammonium or substituted ammonium cation.
  • Suitable level of oxygen bleaches is in the range from 0.01 to 80% wt, preferred level is between 10 and 70% wt, ideally 30 to 60% wt .
  • active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that being reduced to water would be stoichiometrically equivalent to a given percentage concentration of a given peroxide compound, when the peroxide functionality of the peroxide compound is completely reduced to oxides.
  • the active oxygen sources according to the present invention increase the ability of the compositions to remove oxidisable stains, to destroy malodorous molecules and to kill germs.
  • the concentration of available oxygen can be determined by methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumo, C. N. Satterfield and R. L. Wentworth, Reinhold Publishing Corporation, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.
  • Suitable organic and inorganic peroxides for use in the compositions according to the present invention include diacyl and dialkyl peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, persulphuric acid and mixtures thereof .
  • Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalatic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
  • Peroxygen bleaching actives useful for this invention are: percarbonates, perborates, peroxides, peroxyhydrates, persulfates.
  • Preferred compound is sodium percarbonate and especially the coated grades that have better stability.
  • the percarbonate can be coated with silicates, borates, waxes, sodium sulfate, sodium carbonate and surfactants cleaning at room temperature .
  • Bleach activators :
  • compositions may additionally comprise from 0% to 30%wt, preferably from 2% to 20%wt of peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide product peroxyacids .
  • peracid precursors suitable for use in the present invention can be found among the classes of anhydrides, amides, imides and esters such as acetyl triethyl citrate (ATC) described for instance in EP 91 87 0207, tetra acetyl ethylene diamine (TAED) , succinic or maleic anhydrides .
  • the detergent composition comprises contains at least one builders or a combination of them from 0.01 to 80% wt, preferably from 0.1 to 50% wt .
  • builders are described below: - the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures therefore with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components .
  • - borate builders, as well as builders containing borate-forming materials than can produce borate under detergent storage or wash conditions can also be used.
  • - iminosuccinic acid metal salts - polyaspartic acid metal salts. - ethylene dia ino tetra acetic acid and salt forms.
  • phosphate buiders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and salts of phytic acid.
  • water- soluble phosphate builders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
  • Such polymers include the polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates .
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A- 1,389,732, and aminosuccinates described in NL-A-7205873 , and the oxypolycarboxylate materials such as 2-oxa-l,l,3- propane tricarboxylates described in GB-A-1, 387, 447.
  • Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1, 3 , 3-propane tetracarboxylates and 1, 1, 2 , 3-propane tetracarobyxlates.
  • Polycarboxylates contining sulfo substituents include the sulfosuccinate derivatives disclosed in GB-A-1, 398 , 421, GB-A-1, 398, 422 and US-A-3 , 936448 , and the sulfonated pyrolsed citrates described in GB-A-1, 439, 000.
  • Alicylic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5, 6-hexane - hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as s.orbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1, 425, 343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Suitable polymer water-soluble compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two caroxylic radicals separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of thereof.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance .
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1, 379, 241, lactoxysuccinates described in GB-A-1, 389, 732 , and aminosuccinates described in NL-A-7205873 , and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane tricarboxylates described in GB-A-1, 387, 447.
  • succinate derivates such as the carboxymethloxysuccinates described in GB-A-1, 379, 241, lactoxysuccinates described in GB-A-1, 389, 732 , and aminosuccinates described in NL-A-7205873 , and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane
  • Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1, 261, 829, 1,1,2,2- ethane tetracarboxylates, 1 , 1 , 3 , 3-propane tetracarboxylates and 1 , 1 , 2 , 3-propane tetracarobyxlates.
  • Polycarboxylates confining sulfo suibstituents include the sulfosuccinate derivatives disclosed in GB-A- 1,398,421, GB-A-1, 398, 422 and US-A-3 , 936448 , and the sulfonated pyrolsed citrates described in GB-A-1, 439, 000.
  • Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2 , 3 , 4, 5, 6-hexane - hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1, 425, 343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • More preferred polymers are homo-polymers, copolymers and multiple polymers of acrylic, flourinated acrylic, sulfonated styrene, maleic anhydride, metacrylic, iso-butylene, styrene and ester monomers.
  • these polymers are Acusol supplied from Rohm & Haas, Syntran supplied from Interpolymer and Versa and Alcosperse series supplied from Alco Chemical, a National Starch & Chemical Company.
  • bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium and calcium carbonate and sesqui- carbonate and mixtures thereof .
  • carbonate type builders are the metal carboxy glycine and metal glycine carbonate.
  • builders are compounds that sequester metal ions associated with the hardness of water, e.g. calcium and magnesium
  • chelating agents are compounds that sequester transition metal ions capable of catalysing the degradtaion of oxygen bleach systems.
  • certain compounds may have the ability to do perform both functions.
  • Suitable chelating agents to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof. Chelating agents when used, are typically present herein in amounts ranging from 0.01% to 50%wt of the total composition and preferably from 0.05% to 10%wt.
  • Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate) , alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates .
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein ar-e diethylene triamine penta methylene phosphonates.
  • Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST TM.
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al .
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1, 2-dihydroxy -3,5- disulfobenzene .
  • a preferred biodegradable chelating- agent for use herein is ethylene diamine N,N' -disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof .
  • Ethylenediamine N,N' -disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N' -disuccinic acids is, for instance, commercially available under the tradename ssEDDS TM from Palmer Research Laboratories .
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA) ,N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic acid (MGDA) , both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine diacetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS TM and methyl glycine di-acetic acid (MGDA) .
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Fillers useful for the present invention are sodium chloride, bentonite, zeolites, citrates, talc and metal sulfate salts as sodium, calcium and aluminium sulfates. They can be used at a level from 0.01 to 60%wt, preferably between 0.1 to 30%wt.
  • Solvents can be used at levels of 0.01 to 50%wt, preferred level is between 0.1-5%wt.
  • the solvent constituent may include one or more alcohol, glycol, acetate, ether acetate, glycerol, polyethylene glycol with molecular weight ranging from 200 to 10000, silicones or glycol ethers.
  • Exemplary alcohols useful in the compositions of the invention include C2-C8 primary and secondary alcohols which may be straight chained or branched, preferably pentanol and hexanol .
  • Preferred solvents for the invention are glycol ethers and examples include those glycol ethers having the general structure.
  • Preferred solvents for the invention are glycol ethers and examples include those glycol ethers having the general structure R a -0- [CH 2 - CH(R) - (CH 2 ) -0] n -H, wherein Ra is C ⁇ - 20 alkyl or alkenyl, or a cyclic alkane group of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n is an integer from 1 to 10, preferably from 1 to 5; each R is selected from H or CH 3; and a is the integer 0 or 1.
  • Specific and preferred solvents are selected from propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol monoethyl ether acetate, and particularly useful are, propylene glycol phenyl ether, ethylene glycol hexyl ether and diethylene glycol hexyl ether.
  • fragrance selected from a list consisting fragrance, anticaking agent (such as sodium xylene sulfonate and magnesium sulfate) , dye, enzyme are present at levels of up to 5%wt preferably less then l%wt.
  • anticaking agent such as sodium xylene sulfonate and magnesium sulfate
  • the device has been compared with other foam making equipment in terms of time for foam preparation, foam consistency and convenience.
  • the gadget efficacy in foam application onto the stain and cleaning performance have been showed against no gadget usage .
  • the foam has been prepared by dissolving in warm water Oxi Action Max powder, which contains foaming surfactants . About 15 grams of powder has been used with 100 ml of warm water. The solution can be prepared in a 300-500 ml open container.
  • the different devices are compared for preparing the foam.
  • the reference is the spoon that can be used as 5 mixing/aerating device.
  • the devices are rated in terms of timing necessary to prepare the foam, consistency of the foam, convenience in preparing the foam and cost:
  • the stain removal evaluation of standard soils has been done considering Y, the reflectance value has been used for performance evaluation.
  • the X Y Z scale has been used with a spectrophotometer with the UV-filter at 460 nm.
  • Y 100 means a complete stain removal. 0 Standard prepared stains have been used for the test .
  • the cellular plastic device described for preparing the foam was compared to the simple mixing with the spoon, with a hand propeller system, with a 'cappuccino cream maker' , with a shaker and with a battery powered 10 mixer. In all cases 15 grams of Oxi Action Max powder has been dissolved in 100 ml of warm water, prior to using the devices .
  • the cellular plastic device cleaning performance has 15 been compared to just applying the foam onto the stain with a spoon and then rinsing.
  • Foams were prepared by dissolving 15 g in 100 ml of warm water, using Ex 1 and Ref from 1 to 5 gadgets.
  • Multi-use can be used for foam preparation, application onto the stain and for cleaning through scrubbing.
  • the cellular sponge gadget is a manual system that has been rated as the more convenient among the different manual tools, it is very effective in preparing the foam, short time and good foam consistency.
  • the cellular 10 plastic device is in addition quite cheap and it can be used also for foam application onto the stain and for improving the cleaning performance .
  • Results for stain removal 15
  • the cellular plastic device of the present invention was been used to prepare the foam by dissolving 15 g of Vanish Oxi Action Max in 100 ml of water and compared to the use of the spoon. In both cases two grams of the foam 20 were applied onto each standard soiled swatch. In the case of the cellular plastic device 3 scrubbing back and forwards have been conducted on each swatch. Then the foam was left for 10 minutes before rinsing with cold water. After 10 minutes of the foam action all samples 25 were rinsed. For each device /stain for replicates were performed and the values reported in the table below are the average.
  • the stable foam is prepared by dissolving the cleaning formulation , from 1 to 50 grams in 100 ml of water, preferably between 10 and 30 grams into 100ml of water.
  • the stable foam is formed due to the source of active oxygen evolving oxygen within a surfactant .
  • the stain removal evaluation of standard soils has been done considering Y, the reflectance value has been used for performance evaluation.
  • the X Y Z scale has been used 15 with a spectrophotometer with the UV-filter at 460 nm.
  • Standard prepared stains have been used for the test .
  • 20 Standard stains (aged stain) 20 Standard stains (aged stain) :
  • ⁇ E 0 means no colour damage and in general the lower the value the lower the colour damage .
  • the foams described in this invention were prepared by using powder formulations easily produced by mixing in a suitable container the ingredients.
  • the foam was prepared by dissolving 15 grams of the cleaning formulation of this invention in 100 ml of warm water (40°C) and mixing for 3 minutes. The foam was applied for 10 minutes before rinsing with cold water (20°C) .
  • Product available on the market, Oxy Magic from Dr. Beckmann and Oxiclean new from Orange glo were used as references. These two products have been tested with the same procedure even if it was not possible to make a stable foam, but only a solution or a slightly foaming solution.
  • Foams were prepared by using Ex 1, 2 and 3, for all dissolving 15 g and 30 grams in 100 ml of warm water and 5 mixing for 3 minutes .
  • the formulation of present invention have been used as a 10 foam by dissolving 15 g in 100 ml of water and applying 2 ml of the foam onto each stain. After 10 minutes of contact with the foam all samples were rinsed. The reference products were used at the same dosage. Four replicates were made and the values reported in the table 15 below is the average .
  • Oxiclean powder has been used as a reference. Three replicates have been considered for each product/colour type and the values reported in the table below are averages .
  • Ref 1 Oxiclean from Orange glo. * foam made with 15 grams of Ex2 in 100 ml water 1 0 ** foam made with 30 grams of Ex2 in 100 ml water
  • a value of delta E below 3.0 can be considered as no colour damage .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Glass Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne un procédé de traitement d'étoffe qui consiste à produire une mousse stable à partir d'une solution de nettoyage et à appliquer cette mousse stable sur l'étoffe. L'invention concerne également la formulation de nettoyage elle-même, laquelle comprend une source de peroxyde d'hydrogène, par exemple du percarbonate de sodium, et au moins un autre tensioactif.
EP04768525A 2003-10-07 2004-09-16 Procede de nettoyage Expired - Lifetime EP1670890B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0323394A GB0323394D0 (en) 2003-10-07 2003-10-07 Method of removing fabric stains
GB0409178A GB2413336A (en) 2004-04-24 2004-04-24 Method of cleaning using a foam and an aeration device
PCT/GB2004/003979 WO2005040326A1 (fr) 2003-10-07 2004-09-16 Procede de nettoyage

Publications (2)

Publication Number Publication Date
EP1670890A1 true EP1670890A1 (fr) 2006-06-21
EP1670890B1 EP1670890B1 (fr) 2007-08-22

Family

ID=34525041

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04768525A Expired - Lifetime EP1670890B1 (fr) 2003-10-07 2004-09-16 Procede de nettoyage

Country Status (8)

Country Link
EP (1) EP1670890B1 (fr)
AT (1) ATE371012T1 (fr)
AU (1) AU2004284267B2 (fr)
BR (1) BRPI0415071B1 (fr)
DE (1) DE602004008492T2 (fr)
ES (1) ES2288269T3 (fr)
MX (1) MXPA06003969A (fr)
WO (1) WO2005040326A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014199151A3 (fr) * 2013-06-13 2015-02-05 Reckitt Benckiser (Brands) Limited Produit

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2744904C2 (ru) 2016-11-01 2021-03-17 Конинклейке Филипс Н.В. Портативное устройство для удаления загрязнений

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1418889A (en) * 1972-12-20 1975-12-24 Martin P Paint applicators
US4106153A (en) * 1975-07-15 1978-08-15 Lemelson Jerome H Cleaning appliance
US4232420A (en) * 1979-04-23 1980-11-11 Sam Schuster Scouring pad handle
PH23834A (en) * 1985-12-02 1989-11-23 Willson Co Ltd Brush for application of wax
US5866524A (en) * 1994-03-30 1999-02-02 Procter & Gamble Company Foamed cleaning compositions and method of treating textile fabrics
NZ270287A (en) * 1995-01-05 1998-06-26 Jason Robert Jones Sanding aid comprises a handle portion with attached pad and abrasive sheet is releasably attached to the pad
DE19644653A1 (de) * 1996-10-26 1998-04-30 Diversey Gmbh Verfahren und Vorrichtung zur Reinigung von mit Fett-, Stärke- und/oder Eiweißschmutz hochbelasteten Flächen, insbesondere in der Lebensmittelindustrie
US6023810A (en) * 1998-07-28 2000-02-15 Gessert; Roy E. Grill cleaning apparatus incorporating detachable handle and holder for removable scouring pad
US6403547B1 (en) * 1998-10-30 2002-06-11 The Procter & Gamble Company Process of cleaning carpets with a composition comprising peroxygen bleach
WO2000037183A1 (fr) * 1998-12-21 2000-06-29 Wagner Spray Tech Corporation Couche intermediaire en mousse pour applicateurs de peinture en eponge
US20020001636A1 (en) * 2000-06-30 2002-01-03 Greg Holloway Surface texture applicator
US6371675B1 (en) * 2000-12-20 2002-04-16 Becton, Dickinson And Company Skin disinfectant applicator
US20020076258A1 (en) * 2000-12-20 2002-06-20 Crosby Cynthia T. Skin disinfectant applicator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005040326A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014199151A3 (fr) * 2013-06-13 2015-02-05 Reckitt Benckiser (Brands) Limited Produit

Also Published As

Publication number Publication date
AU2004284267B2 (en) 2010-02-04
EP1670890B1 (fr) 2007-08-22
ES2288269T3 (es) 2008-01-01
DE602004008492T2 (de) 2008-05-15
ATE371012T1 (de) 2007-09-15
AU2004284267A1 (en) 2005-05-06
MXPA06003969A (es) 2006-06-27
WO2005040326A1 (fr) 2005-05-06
BRPI0415071B1 (pt) 2014-12-30
BRPI0415071A (pt) 2006-11-28
DE602004008492D1 (de) 2007-10-04

Similar Documents

Publication Publication Date Title
CA1059267A (fr) Methode de blanchiment
GB2321251A (en) Carpet cleaning and treatment compositions
GB2129456A (en) Stabilized bleaching and laundering composition
AU2004284267B2 (en) Method of cleaning
GB2413336A (en) Method of cleaning using a foam and an aeration device
AU2013223806B2 (en) Product
ZA200602660B (en) Method of cleaning
WO2005040321A1 (fr) Combinaison synergique d'agents tensioactifs
EP2126021B1 (fr) Composition et procédé
GB2406574A (en) Extruded fabric cleaning bar
GB2544470B (en) Laundry composition
WO2007119054A1 (fr) Composition et procédé
EP1994131A1 (fr) Composition et procede
CA2552051A1 (fr) Composition de traitement de tapis
WO2014199151A2 (fr) Produit
WO2007119053A1 (fr) Composition et procédé de nettoyage
WO2007057697A1 (fr) Formulations nettoyantes solides
WO2007093817A1 (fr) Composition detergente

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060330

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20060621

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RECKITT BENCKISER N.V.

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602004008492

Country of ref document: DE

Date of ref document: 20071004

Kind code of ref document: P

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004008492

Country of ref document: DE

Effective date: 20071004

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2288269

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071122

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070930

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080122

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071122

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

26N No opposition filed

Effective date: 20080526

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004008492

Country of ref document: DE

Effective date: 20080526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070917

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080223

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070822

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: RECKITT BENCKISER VANISH B.V.

Effective date: 20160321

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602004008492

Country of ref document: DE

Representative=s name: BARDEHLE PAGENBERG PARTNERSCHAFT MBB PATENTANW, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 602004008492

Country of ref document: DE

Owner name: RECKITT BENCKISER VANISH B.V., NL

Free format text: FORMER OWNER: RECKITT BENCKISER N.V., HOOFDDORP, NL

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: RECKITT BENCKISER VANISH B.V., NL

Effective date: 20160411

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20160721 AND 20160727

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20180919

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20181001

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190916

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190917

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230513

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230727

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230710

Year of fee payment: 20

Ref country code: DE

Payment date: 20230726

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602004008492

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20240915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240915