EP2622056B1 - Composition de detergent - Google Patents

Composition de detergent Download PDF

Info

Publication number
EP2622056B1
EP2622056B1 EP11760487.6A EP11760487A EP2622056B1 EP 2622056 B1 EP2622056 B1 EP 2622056B1 EP 11760487 A EP11760487 A EP 11760487A EP 2622056 B1 EP2622056 B1 EP 2622056B1
Authority
EP
European Patent Office
Prior art keywords
oil
weight
composition according
pap
composition
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.)
Active
Application number
EP11760487.6A
Other languages
German (de)
English (en)
Other versions
EP2622056A1 (fr
Inventor
Arun Kumar Nagarajan
Deeleep Kumar Rout
Ritesh Kumar Sinha
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=44674803&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2622056(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP11760487.6A priority Critical patent/EP2622056B1/fr
Publication of EP2622056A1 publication Critical patent/EP2622056A1/fr
Application granted granted Critical
Publication of EP2622056B1 publication Critical patent/EP2622056B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • C11D17/0021Aqueous microemulsions
    • 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
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • 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
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention is in the field of detergent compositions; in particular high active liquid detergent compositions, for use in laundry and/or household cleaning amongst others.
  • the compositions of the present invention relate to the field of water-in-oil micro-emulsions.
  • Liquid detergent compositions are widely appreciated and preferred by many modern day consumers in both developed and developing and emerging markets. Such liquid detergent compositions are primarily used in Laundry and household care applications.
  • Liquid detergent compositions are widely known in the art.
  • Liquid detergent compositions generally comprise a surfactant active and a solvent.
  • Liquid detergent compositions may further comprise perfume, builder, polymers, bleach, thickeners, fluorescers, and other common detergent ingredients.
  • Liquid detergent compositions are often structured, e.g. to control the viscosity of the liquid or to improve stability and prevent phase separation or to be able to incorporate ingredients that are water insoluble.
  • Present day liquid detergent compositions typically do not contain bleach and therefore do not work well on bleachable stains, such as coffee, tea, tomato and wine.
  • current liquid detergent products contain only low levels of surfactant, and therefore also do not meet the consumers' requirement for the removal of oily and fatty stains.
  • a stable liquid detergent composition is a detergent composition in the form of an emulsion.
  • a defined kind of emulsion is the micro-emulsion.
  • emulsions are opaque liquids which are not appreciated by modern day consumers.
  • Micro-emulsions can be made transparent and typically have a lower viscosity too.
  • WO95/27034 discloses detergent compositions in the form of oil in water micro-emulsions providing rapid stain removal.
  • the composition of WO95/27034 comprises a surfactant system comprising short chain length non-ionic alcohol ethoxylates having less than 12 carbon atoms and with at least 45% of C10 material. It is found that these oil in water micro-emulsions do not provide adequate dissolution of fatty stains and soils when applied neat. Fast fat (or oily soil) solubilisation when applied neat onto a fatty stain or soil remains to be desired for amongst other the dissolution of sebum on shirt collars and fatty soils on hard surfaces.
  • Micro-emulsions have also been disclosed in a number of other documents such as US 5,415,812 , which discloses a light duty detergent composition; or US 4,438,009 , which discloses low solvent laundry pre-treatment compositions.
  • EP-A2-610 010 bleach containing micro emulsions have been disclosed, however, this disclosure relates to an o/w (oil in water) microemulsion.
  • the continuous phase is aqueous, it's efficacy in solubilising fatty solids leaves to be desired.
  • US20070117734 discloses liquid-crystalline washing or cleaning compositions containing PAP in particulate form.
  • laundry pre-treatment compositions are disclosed in the form of micro-emulsions. It discloses mixtures of polyamines and grease cutting solvents. Other surfactants such as non-ionic surfactants are also disclosed.
  • liquid detergent composition that removes soils and/or stains of solid or solidified fatty material in the main wash at neutral pH.
  • a water-in-oil micro-emulsion detergent composition as described by claim 1, comprising a hard water tolerant surfactant, water, oil and phtaloyl amino peroxycaproic acid
  • PAP provides a concentrated liquid bleaching detergent composition that removes soils and/or stains of solid or solidified fatty material in the main wash at neutral pH.
  • the present invention provides a water-in-oil micro-emulsion detergent composition
  • a surfactants system comprising 20-75% by weight of a surfactants system; 5-20% by weight of an aqueous solution having an ionic strength of 0.01 - 4 mol/L comprising: water; and an electrolyte, excluding surfactant system (a); 10-40 % by weight of a saturated oil; and 0.1-10% by weight of phthaloyl-amino-peroxycaproic acid (PAP); and wherein the composition comprises less than 100 ppb of transition metal ions, and wherein the pH is between 4 and 8.
  • a surfactant system a
  • PAP phthaloyl-amino-peroxycaproic acid
  • the invention provides a process for preparing a micro-emulsion according to any one of claims 1 to 7 comprising the steps in sequence of: adding in the surfactant system to a oil/solvent, mixing them together by an overhead stirrer, adding the PAP and mixing again; adding optional hydrophobic ingredients, and adding aqueous phase containing electrolytes.
  • the invention relates to water-in-oil (w/o) micro-emulsion detergent composition.
  • a water-in-oil micro-emulsion has a configuration comprising discrete droplets of water in oil.
  • These w/o microemulsions are also characterised by a low electrical conductivity values, preferably ⁇ 1 mS/cm, more preferably ⁇ 0.1 mS/cm, (e.g. measured with a conductivity meter; (e.g. Orion 150)).
  • the water volume fraction in the microemulsion is typically ⁇ 0.2, to avoid percolation of water droplets leading to a higher electrical conductivity of the sample.
  • Typical water droplet diameters are in the range of 2 - 50 nm (e.g.
  • the viscosity is in the range of 30 - 300 CP (measured at 20 sec 1 , using a controlled stress rheometer, CSL 500 TA Instruments).
  • compositions according to the invention comprise 20 to 75% by weight of the composition of a surfactant.
  • Hard water tolerant surfactants such as alkyl ether sulphates (e.g. SLES), Alkyl polyether carboxylates, esters and amides of fatty acids, alkane sulphonates, Polyoxyalkylene phosphate esters, phosphated and polyphosphated alcohols, sulfosuccinates (di-2-ethylhexyl sulfosuccinates) alkoxylated non-ionic surfactants (e.g., lauryl alcohol ethoxymers), EO/PO block copolymers, Alkyl polyglucosides (APGs), Alkyl N-methyl glucamides, Amine oxides, Amine ethoxylates, Methyl ester ethoxylates, alkanol amides, Amidopropyl amines, carboxybetaines, Sulfo- and phosphor-betaines, Aminoethylethanolamine-derived amphoterics
  • the most preferred hard water tolerant surfactants are alkoxylated non-ionic surfactants, Alkyl ether sulfates, Alkyl polyglucosides and mixtures thereof.
  • the surfactant is preferably present in a concentration of at least 30%, more preferably at least 40%, still more preferably at least 50%, or even at least 60% by weight of the composition.
  • the surfactant is preferably present in a concentration of not more than less than 70% by weight of the composition.
  • hard water tolerant surfactants may be found in well known textbooks like " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , and/or the current edition of " McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • anionic and non-ionic surfactants are most preferred, while any surfactant may be used in household cleaning compositions.
  • the linear or branched alkoxylated fatty alcohol having a carbon chain of between 10 and 16 carbon atoms are preferred in the composition.
  • the fatty alcohol is preferably ethoxylated, having an average of between 0 and 7 EO groups.
  • anionic and non-ionic surfactants are the most preferred.
  • hard surface spray cleaner spray and wipe
  • any surfactant may be used.
  • High active compositions even preferably comprise at least 50% by weight, more preferably at least 60% by weight or even at least 70% by weight of the surfactant system.
  • liquid laundry or fabric cleaning compositions, fabric conditioning compositions and household cleaning compositions typically comprise not more than 75% by weight, more preferably not more than 70% by weight, still more preferably not more than 60% by weight, or even not more than 50% by weight.
  • the composition comprises 5-20% by weight of an aqueous solution, having an ionic strength of from 0.01 to 4 mol/l, preferably at least 0.05 mol/l, preferably at least 0.1 mol/l, preferably at least 0.2 mol/l, or even at least 0.5 mol/l, but preferably not more than 3.5 mol/l, or even not more than 3 mol/l.
  • the aqueous composition comprises water and an electrolyte for improved performance.
  • the electrolyte is typically present in the composition in such a concentration that the ionic strength is in the above given range. Typically the electrolyte is present in a concentration of up to 15 % by weight based on the aqueous solution, when the electrolyte is a mono-valent electrolyte salt. The required amount is dependent on the type of electrolyte used and its valance.
  • monovalent cationic salt are preferably present in a concentration of between 1 and 15% based on the aqueous solution, while divalent cationic salt are preferably present in a concentration of between 0.01 and 4% based on the aqueous solution, and trivalent and multivalent cationic salt are preferably present in a concentration of between 0.005 and 2% based on the aqueous solution.
  • Preferred electrolytes are phosphates, sulphates of alkali metal and alkaline earth metals mixtures of any of the above.
  • Preferred trivalent metal cation is Al 3+ .
  • transition metal cations are excluded as they are detrimental to bleach stability.
  • Hydroxide salts are not preferred, due to unfavourable pH effects and undesirable reactions.
  • the composition further comprises 10 to 40% by weight of a saturated oil.
  • the oil is a saturated, linear, branched or cyclic hydrocarbon with MP >-100 °C, selected from the following class of chemicals: (i) esters; (ii) acids and (iii) triglycerides and (iv) alkanes.
  • the oil preferably has a Hansen solubility of between 14 and 20 (MPa) 0.5 .
  • the Hansen solubility is preferably at least 15 (MPa) 0.5 , more preferably at least 16 (MPa) 0.5 , and typically not more than 19 (MPa) 0.5 or even not more than 18 (MPa) 0.5 .
  • the oil preferably has a solubility of solid triglyceride fatty matter into the oil and/or solvent of more than 3% by weight.
  • the solubility of solid trilaurin (a triglyceride) fatty matter into the oil is more than 5%, or even more than 10%. This percentage is based on the aggregate amount of the oil and the trilaurin dissolved therein.
  • the oil is preferably selected from alkyl-, aryl- esters of saturated fatty acids, saturated fatty acid oils, mono- di- and tri-glycerides without any unsaturations, sugar derived polyesters and sucrose polyesters.
  • Preferred fatty acids are C8-22 fatty acids and including di- and tri-carboxylic acids and oligomeric fatty acids (such as commercially available as Pripol 1017 ex. Unichema).
  • Preferred triglycerides include those of medium chain glycerides, which are liquid at ambient conditions are also contemplated.
  • oils from renewable sources such as oil derived from palms, soy, coconut and jatropha.
  • the bleach according to the invention is phthaloyl-amino-peroxycaproic acid (also referred to in literature as N-N-phthaloyl-amino-peroxycaproic acid, phthalimido perhexanoic acid or simply as PAP) is an oil soluble organic peracid and it is incorporated in to the composition up to 10 % by weight, preferably up to 8% by weight, more preferably up to 5% by weight; and is present in a concentration of at least 0.1%, more preferably at least 0.5% still more preferably at least 1%, or even at least 2% by weight of the composition.
  • PAP phthaloyl-amino-peroxycaproic acid
  • the PAP is preferably solubilised in the oil/solvent phase of the water-in-oil micro-emulsion. It is expected that the PAP acts on soil during the interaction of oil droplets with the soiled substrates.
  • the pH of the composition is acidic to neutral, by which is meant that the pH is between 4 and 8. The best results with compositions wherein PAP is incorporated, are obtained when the pH is in the range of 5 to 7.
  • composition may further comprise builder, anti-redeposition agents, mosquito and/or insect repellents, shading dyes, antimicrobial agents (oil based), oil-soluble fluorescer, enzymes, perfumes and soil release polymers.
  • Perfume may be incorporated in the composition in a concentration of between 0.1 and 5% by weight. Typically the concentration is less than 3%, even less than 2%; generally the perfume is present in a concentration of between 0.5 and 1% by weight. It is demonstrated that perfume incorporated in a micro-emulsion provides up to 10 times better deposition on fabrics and the perfume remains for a longer period compared to only surfactant solution containing equivalent amount of perfume.
  • the viscosity of the composition is preferably low. By low is meant not more than 1000 mPa.s, more preferably not more than 500 mPa.s, preferably less than 300 mPa.s, still more preferably less than 200 mPa.s, or even less than 150 mPa.s. It is preferred that the composition has a viscosity of more than 5 mPa.s, more preferably more than 10 mPa.s, still more preferably more than 20 mPa.s or even more than 50 mPa.s. All viscosities mentioned are measured by a Carrimed CSL-500 rheometer with standard cone and plate geometry, at 20 sec -1 and 25°C.
  • the pH is in a range of 4 to 8, preferably at least 5 and not more than 7. Any known pH adjustment agents or buffer may be used when required.
  • micro-emulsion is made by adding in sequence the surfactant system to a oil/solvent, mixing them together by an overhead stirrer, adding optional hydrophobic ingredients such as fluorescer, bleach and essential oils/perfumes; adding aqueous phase containing electrolytes and adding enzymes/bleaches.
  • Optional hydrophobic ingredients include fluorescer, perfume and water insoluble soil release polymers (e.g. gerol, trademark ex Rhodia).
  • the laundry product may be packaged in a standard bottle.
  • Pre-spotting products are typically filled into a dispensing device, such as, stain pens, roller balls, brush pens, and/or spays dispensers (e.g. trigger spray dispensers or squeeze bottles).
  • Household cleaning products are typically in the form of trigger sprays.
  • Dishwashing liquids are typically sold in bottles.
  • the diagram shows the different kinds of liquids/emulsions that may be obtained and the preferred region (shaded area) of the water in oil microemulsion (W/O-ME) on the right.
  • L ⁇ stands for Liquid Crystalline phases
  • L2 stands for Reversed Micellar Phases
  • L1 stands for Micellar Phases
  • ⁇ E stands for Microemulsion.
  • Example 1 preparation of PAP containing micro-emulsions
  • the PAP may be obtained in pure form or obtained by suspending commercially available 17%w PAP suspension in water using stabilisers and structurants (ex Solvay, Italy), followed by extraction of PAP from the commercial source by using chloroform.
  • the percentage purity of the extracted PAP is 90-92 %w.
  • Non-ionic surfactant e.g. Galaxy 257 (C 12-15 EO ⁇ 7> )
  • the mixture is stirred until a clear solution is obtained.
  • De-ionised water is added and shaken well to get the required formulation.
  • the composition of the formulation is chosen from the phase regions, given in the ternary diagram (see Figure 1 ).
  • compositions according to the invention are given in the table below.
  • Table 1 Compositions 1 2 3 4 A Chemical %w %w %w %w %w %w C12EO7 (Alcohol Ethoxylate) 70 70 59 70 73 Methyl decanoate 13 18 20 12.8 13.5 Water 13 8 20 12.8 13.5 PAP (90-92% pure) 4 4 1 4 Na2SO4 (electrolyte) 0.4
  • composition 4 compositions according to the invention
  • compositions 1-3 and A compositions according to the invention
  • PAP is not stable in aqueous compositions, while it is reasonably stable in organic solvents.
  • the PAP stability in microemulsion compositions comprising water is yet to be determined.
  • the level of PAP in the product is determined by the titration under acidic conditions against thiosulfate/KI according to the following method.
  • a known quantity (g) of the liquid prototype containing PAP is taken. 30ml of isopropanol is added to dissolve the contents. Later on, 50ml of deionised (DI) water is added, followed by 20 ml of glacial acetic acid. The mixture is stirred well. 3 g of potassium iodide (KI) salt is weighed and added to the solution mixture.
  • DI deionised
  • KI potassium iodide
  • the oxygen liberated from PAP oxidizes iodide (I - ) to I 2 .
  • This liberated iodine is estimated using standardized sodium thiosulfate solution, which directly corresponds to the amount of PAP initially present in the solution.
  • % PAP V ml * N * 277 / 2 * 100 1000 * W
  • composition 1 (not according to the invention) was used and stored for over 2 months. Samples were taken according to table 2 and analysed as indicated above. The results are shown in table 2 below. Table 2: PAP microemulsion degradation Days PAP concentration (%wt) 0 3.69 3 3.26 10 2.65 18 2.23 25 2.27 31 1.54 67 0.76
  • the PAP degradation follows a first order reaction kinetics with half life of about 30 days.
  • Example 3 Washing experiment with PAP containing bleach formulation:
  • composition 1 (not according to the invention) and without PAP (comparative composition A) were directly applied on to the fabric on equal active basis that could sufficiently cover the stain spot area. After leaving it in air for two minutes, the fabrics were soaked in 24 °FH water at 25 °C for 30 min and then washed in a terg-o-tometer (7243 Es) for 15 min, followed by rinsing for two min two times. The UC was maintained at 20 and spindle rpm at 80-90.
  • Table 3a Tea stains results Comp A Comp 1 dR 460 SD dR 460 SD Cotton 22.345 0.684 30.904 1.398 Polycotton 32.638 0.740 35.943 0.624 Polyester 36.375 0.631 42.643 1.230
  • Table 3b Grass stains results Comp A Comp 1 dR 460 SD dR 460 SD Cotton 27.346 0.467 31.785 0.346 Polycotton 24.133 3.111 34.144 0.686 Polyester 36.035 2.444 38.801 0.556

Landscapes

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

Claims (10)

  1. Composition détergente de type micro-émulsion eau dans l'huile comprenant
    a. 20 à 75 % en poids d'un système de tensioactifs ;
    b. 5 à 20 % en poids d'une solution aqueuse ayant une force ionique de 0,01 à 4 mol/L comprenant :
    i de l'eau ; et
    ii un électrolyte, exclusion faite du système de tensioactifs (a)
    c. 10 à 40 % en poids d'huile saturée ; et
    d. 0,1 à 10 % en poids d'acide phtaloyl-amino-peroxycaproïque (PAP) ; et
    dans laquelle la composition comprend moins de 100 ppb d'ions métalliques de transition, et dans laquelle le pH est entre 4 et 8.
  2. Composition selon la revendication 1, dans laquelle l'huile saturée est choisie parmi les esters d'acides gras, les huiles d'acides gras, les triglycérides, les polyesters dérivés de sucres et les polyesters saccharosiques et leurs mélanges.
  3. Composition selon l'une quelconque des revendications 1 ou 2, dans laquelle l'huile a une solubilité de Hansen entre 14 et 20 (MPa)0,5.
  4. Composition selon la revendication 3, dans laquelle la solubilité de Hansen est entre 16 et 18 MPa0,5.
  5. Composition selon l'une quelconque des revendications 3 ou 4, dans laquelle la solubilité d'une matière grasse solide de type trilaurine dans l'huile est supérieure à 3 % en poids.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle la solution aqueuse a une force ionique de 0,1 à 4 mol/L.
  7. Composition selon l'une quelconque des revendications précédentes, comprenant en outre un parfum.
  8. Pulvérisateur à gâchette comprenant la composition selon l'une quelconque des revendications 1 à 7.
  9. Dispositif de pré-détachage choisi parmi les crayons, les stylos à bille et les brosses de détachage, comprenant la composition selon l'une quelconque des revendications 1 à 7.
  10. Procédé de préparation d'une micro-émulsion selon l'une quelconque des revendications 1 à 7 comprenant les étapes successives consistant à :
    a ajouter le système de tensioactifs à une huile/solvant,
    b les mélanger ensemble à l'aide d'un agitateur de tête,
    c ajouter le PAP et mélanger de nouveau,
    d ajouter les ingrédients hydrophobes facultatifs
    e ajouter la phase aqueuse contenant les électrolytes.
EP11760487.6A 2010-09-28 2011-09-23 Composition de detergent Active EP2622056B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11760487.6A EP2622056B1 (fr) 2010-09-28 2011-09-23 Composition de detergent

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN2688MU2010 2010-09-28
EP10191813 2010-11-19
PCT/EP2011/066578 WO2012041774A1 (fr) 2010-09-28 2011-09-23 Composition de détergent
EP11760487.6A EP2622056B1 (fr) 2010-09-28 2011-09-23 Composition de detergent

Publications (2)

Publication Number Publication Date
EP2622056A1 EP2622056A1 (fr) 2013-08-07
EP2622056B1 true EP2622056B1 (fr) 2014-07-02

Family

ID=44674803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11760487.6A Active EP2622056B1 (fr) 2010-09-28 2011-09-23 Composition de detergent

Country Status (7)

Country Link
EP (1) EP2622056B1 (fr)
CN (1) CN103119147B (fr)
BR (1) BR112013007234A2 (fr)
EA (1) EA022865B1 (fr)
ES (1) ES2511465T3 (fr)
WO (1) WO2012041774A1 (fr)
ZA (1) ZA201302499B (fr)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4438009A (en) 1981-08-14 1984-03-20 S. C. Johnson & Son, Inc. Low solvent laundry pre-spotting composition
US4561991A (en) 1984-08-06 1985-12-31 The Procter & Gamble Company Fabric cleaning compositions for clay-based stains
US4919839A (en) 1989-02-21 1990-04-24 Colgate Palmolive Co. Light duty microemulsion liquid detergent composition containing an aniocic/cationic complex
GB9302015D0 (en) * 1993-02-02 1993-03-17 Unilever Plc Improvements to hygiene compositions
ES2147217T3 (es) * 1993-11-12 2000-09-01 Unilever Nv Composicion detergente.
CA2173137A1 (fr) 1994-03-31 1995-10-12 Peter Robert Garrett Compositions detergentes
DE10359247B3 (de) * 2003-12-17 2005-07-28 Seitz Gmbh Flüssige Bleich- und/oder Desinfektionsmittel-Zusammensetzung und deren Anwendung
DE102004019139A1 (de) * 2004-04-16 2005-11-10 Henkel Kgaa Flüssigkristallines Wasch- oder Reinigungsmittel mit teilchenförmigem Bleichmittel

Also Published As

Publication number Publication date
EA201300409A1 (ru) 2013-08-30
CN103119147B (zh) 2014-11-19
CN103119147A (zh) 2013-05-22
WO2012041774A1 (fr) 2012-04-05
ZA201302499B (en) 2014-06-25
ES2511465T3 (es) 2014-10-22
EP2622056A1 (fr) 2013-08-07
EA022865B1 (ru) 2016-03-31
BR112013007234A2 (pt) 2016-06-14

Similar Documents

Publication Publication Date Title
EP2513277B1 (fr) Composition détergente sous forme de microémulsion bi-continue
KR102017917B1 (ko) 항복점 ii를 갖는 구조화 세제 또는 세정제
US9187714B2 (en) Structured liquid detergent or cleaning agent having a flow limit and inorganic salt
US11814604B2 (en) Cleaning compositions employing extended chain anionic surfactants
EP2379689B1 (fr) Émulsion extrêmement visqueuse de détergent
EP2877564B1 (fr) Composition de détergent liquide
EP3847229B1 (fr) Composition de nettoyage moussante
EP2622056B1 (fr) Composition de detergent
EP2782987B1 (fr) Composition de détergent liquide
EP3458565A1 (fr) Composition de prétraitement pour les taches sur les textiles
EP2361963A1 (fr) Composition de détergent à micro-émulsion bi-continue
EP3365416B1 (fr) Composition et procede pour traiter des substrats
DE102016204268A1 (de) Waschmittelzusammensetzung

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: 20130220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

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

INTG Intention to grant announced

Effective date: 20140321

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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM 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

Ref country code: AT

Ref legal event code: REF

Ref document number: 675943

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011008178

Country of ref document: DE

Effective date: 20140814

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2511465

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20141022

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 675943

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140702

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140702

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: LT

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: 20140702

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: 20141003

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: 20141103

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: 20140702

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: 20141002

Ref country code: NO

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: 20141002

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: 20140702

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: 20140702

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

Ref country code: IS

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: 20141102

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: 20140702

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: 20140702

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: 20140702

Ref country code: LV

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: 20140702

Ref country code: HR

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: 20140702

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: 20140702

Ref country code: RS

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: 20140702

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011008178

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140923

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: 20140702

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: 20140702

Ref country code: MC

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: 20140702

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: 20140702

Ref country code: IT

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: 20140702

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: 20140702

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20150402

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011008178

Country of ref document: DE

Effective date: 20150402

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 NON-PAYMENT OF DUE FEES

Effective date: 20140930

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

Ref country code: LI

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

Effective date: 20140930

Ref country code: CH

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

Effective date: 20140930

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: 20140923

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20140702

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

Ref country code: SM

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: 20140702

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

Ref country code: MT

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: 20140702

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; INVALID AB INITIO

Effective date: 20110923

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: 20140702

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: CH

Ref legal event code: PK

Free format text: DAS PRIORITAETSAKTENZEICHEN WURDE BERICHTIGT: 2668MU2010/28.09.2010

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602011008178

Country of ref document: DE

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

27O Opposition rejected

Effective date: 20170616

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

Ref country code: MK

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: 20140702

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

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

Ref country code: AL

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: 20140702

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

Ref country code: FR

Payment date: 20190927

Year of fee payment: 9

Ref country code: DE

Payment date: 20190918

Year of fee payment: 9

Ref country code: TR

Payment date: 20190916

Year of fee payment: 9

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

Ref country code: GB

Payment date: 20190920

Year of fee payment: 9

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

Ref country code: ES

Payment date: 20191022

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011008178

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200923

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

Ref country code: FR

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

Effective date: 20200930

Ref country code: DE

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

Effective date: 20210401

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 NON-PAYMENT OF DUE FEES

Effective date: 20200923

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220119

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: 20200924