[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP2791308B1 - Compositions pour lessiver - Google Patents

Compositions pour lessiver Download PDF

Info

Publication number
EP2791308B1
EP2791308B1 EP12781306.1A EP12781306A EP2791308B1 EP 2791308 B1 EP2791308 B1 EP 2791308B1 EP 12781306 A EP12781306 A EP 12781306A EP 2791308 B1 EP2791308 B1 EP 2791308B1
Authority
EP
European Patent Office
Prior art keywords
polymer
composition according
cationic
carboxylic acid
alkyl ether
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
EP12781306.1A
Other languages
German (de)
English (en)
Other versions
EP2791308A1 (fr
Inventor
Martin Charles Crossman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP12781306.1A priority Critical patent/EP2791308B1/fr
Publication of EP2791308A1 publication Critical patent/EP2791308A1/fr
Application granted granted Critical
Publication of EP2791308B1 publication Critical patent/EP2791308B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to a laundry composition. More particularly, the invention is directed to a liquid laundry detergent composition.
  • One such formulation comprises a cationic polymer and anionic surfactant.
  • Such compositions are known from WO10/072628 A1 which discloses particular combinations of cationic polymers, anionic and nonionic surfactants and fatty acids, with a particular ratio of nonionic surfactant to fatty acid for improved stability.
  • the invention is directed to a laundry liquid detergent composition
  • a laundry liquid detergent composition comprising:-
  • the detergent composition has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.
  • the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%.
  • Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1: wherein R denotes a saturated or unsaturated C 6 -C 22 alkyl chain; R 1 and R 2 are either both hydrogen; or R 1 is hydrogen and R 2 is CH 3 ; or R 1 is CH 3 and R 2 is hydrogen; R 3 is hydrogen, or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium; and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.
  • Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C 8 -C 18 alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof.
  • the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units.
  • a preferred level of the cationic polysaccharide polymer is from 0.1 to 1 wt.%.
  • Preferred cationic polysaccharide polymers are cationic guar and cationic cellulose polymers. Particularly preferred is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose).
  • the composition further comprises an ingredient selected from, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
  • the invention is directed to laundry compositions containing alkyl ether carboxylic acid or carboxylate salt thereof, a cationic polysaccharide polymer, a nonionic surfactant which comprises an alcohol ethoxylate, and an anionic surfactant.
  • the composition displays improved stability over the prior art at pH levels of 6.2 to 9.
  • the invention may take any of a number of forms, particularly those that are intended as laundry main wash products. It can take the form of a laundry treatment agent for the main wash, which may be dilutable or non-dilutable.
  • the laundry treatment agent may for example be an isotropic liquid, or a surfactant-structured liquid.
  • the invention may also take the form of a viscous liquid, for example a gel. Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".
  • the detergent composition has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.
  • composition comprises 1 to 12 wt.% alkyl ether carboxylic acid or carboxylate salt thereof.
  • alkyl ether carboxylic acid/carboxylate is usually derived from a fatty alcohol which is alkoxylated, usually with ethylene glycol and/or propylene glycol, a carboxylic acid is then introduced to the material to form the alkyl ether carboxylic acid.
  • the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%.
  • Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1: wherein R denotes a saturated or unsaturated C 6 -C 22 alkyl chain; R 1 and R 2 are either both hydrogen (in which case the repeat unit is ethylene glycol known as (EO) for short); or R 1 is hydrogen and R 2 is CH 3 ; or R 1 is CH 3 and R 2 is hydrogen (in which case the repeat unit is propylene glycol, known as (PO) for short); R 3 is hydrogen (in which case it is an alkyl ether carboxylic acid), or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium (in which case it is an alkyl ether carboxylate salt); and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.
  • R denotes a saturated or unsaturated C 6 -C 22 alkyl chain
  • R 1 and R 2 are either both hydrogen (
  • Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C 8 -C 18 alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof.
  • the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units.
  • a preferred salt is sodium.
  • suitable materials are oleyl alkyl ether (8EO) carboxylic acid, or laureth-5 carboxylic acid (5EO), and the sodium salts thereof.
  • the liquid detergent composition comprises nonionic surfactant, and anionic surfactant.
  • the nonionic surfactant component comprises alcohol ethoxylate.
  • the alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide.
  • ethylene oxide is reacted with ethylene oxide in the required molar amount to produce the alcohol ethoxylate.
  • Preferred alcohol ethoxylates have from 2 to 40, preferably from 3 to 30, more preferably from 5 to 20 ethylene oxide units attached to the aliphatic chain.
  • the surfactants may be chosen from the surfactants described in " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in 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 .
  • the surfactants used are saturated.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are C 6 to C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used can be water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant may also include soaps of C 6 -C 22 fatty acids.
  • the preferred anionic detergent compounds are sodium C 11 to C 15 alkyl benzene sulphonates and sodium C 12 to C 18 alkyl sulphates. Salts of sulphonates included as hydrotrobes can additionally be considered as anionic surfactants as defined herein. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever ), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 , and alkyl monoglycosides.
  • the nonionic detergent is present in amounts of from 2 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the anionic surfactant is present in amounts of from 4 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the total amount of surfactant present in the liquid composition is preferably at least 6 wt.%, more preferably at least 10 wt.%, more preferably the total amount of surfactant is from 15 to 65 wt.%, preferably from 10 to 50 wt.%.
  • surfactants such as amphoteric, zwitterionic and cationic surfactants may also be present in addition to the aforementioned nonionic and anionic surfactants.
  • This term refers to polymers having an overall positive charge.
  • the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer.
  • the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose.
  • the composition may include a single cationic polysaccharide polymer or a mixture of cationic polymers, providing that at least one of them is a cationic polysaccharide polymer.
  • cationic polysaccharide polymer refers to polymers having a polysaccharide backbone and an overall positive charge.
  • Polysaccharides are polymers made up from monosaccharide monomers joined together by glycosidic bonds.
  • the cationic polysaccharide-based polymers present in the compositions of the invention have a modified polysaccharide backbone, modified in that additional chemical groups have been reacted with some of the free hydroxyl groups of the polysaccharide backbone to give an overall positive charge to the modified cellulosic monomer unit.
  • a preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt.
  • the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group.
  • the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents.
  • Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred.
  • Guar is a galactomannan having a ⁇ -1,4 linked mannose backbone with branchpoints to ⁇ -1,6 linked galactose units.
  • Suitable cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc.
  • guar 2-hydroxy-3-(trimethylammonium) propyl ether salt is guar 2-hydroxy-3-(trimethylammonium) propyl ether salt.
  • Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via ⁇ -1,4 glycosidic bonds and is a linear, non-branched polymer.
  • Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquaternium 10 and is commercially available from the Amerchol Corporation, a subsidiary of The Dow Chemical Company, marketed as the Polymer LR, JR, and KG series of polymers.
  • Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. These materials are available from Amerchol Corporation marketed as Polymer LM-200.
  • Typical examples of preferred cationic cellulosic polymers include cocodimethylammonium hydroxypropyl oxyethyl cellulose, lauryldimethylammonium hydroxypropyl oxyethyl cellulose, stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and stearyldimethylammonium hydroxyethyl cellulose; cellulose 2-hydroxyethyl 2-hydroxy 3-(trimethyl ammonio) propyl ether salt, polyquaternium-4, polyquaternium-10, polyquaternium-24 and polyquaternium-67 or mixtures thereof.
  • the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by the Amerchol Corporation under the trade name UCARE.
  • the counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate.
  • the species responsible for providing a softening benefit in these formulations is a polymer/surfactant complex, especially a cationic polysaccharide polymer/AEC complex.
  • the cationic polysaccharide polymer is present at a level of from 0.1 to 1.5 wt.%, preferably from 0.1 to 1 wt.%, more preferably from 0.2 to 1 wt.%.
  • the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights.
  • the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 10,000 to 500,000 Daltons.
  • the liquid detergent composition may optionally comprise one or more of the following optional ingredients, enzyme, antiredeposition polymer, dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid.
  • DEQUEST TM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN TM .
  • SOKALAN TM Another suitable builder is sodium carbonate.
  • the builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition.
  • the preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
  • Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used are preferably blue or violet.
  • the shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.
  • the dye bears at least one sulfonate group.
  • Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
  • the shading dye is present in the liquid composition in range from 0.0001 to 0.01 wt %.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more polymers.
  • Polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.
  • the composition may comprise one or more polymers.
  • polymers are carboxymethylcellulose, hydroxyethyl cellulose, hydroxpropyl cellulose, poly(ethylene glycol), poly(vinyl alcohol), ethoxylated polyamines, polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Modern detergent compositions typically employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
  • dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof, and are usually present at a level of from 0.01 to 10 wt.% based on total amount in the laundry composition.
  • Anti-redeposition polymers are designed to suspend or disperse soil.
  • antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, Acrylic acid based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF.
  • suitable soil release polymers include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany).
  • Further suitable soil release polymers of a different type include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). If present, the soil release polymer may be included at a level of from from 0.01 to 10 wt.% based on total amount in the laundry composition.
  • Further examples of soil release polymers are terephthalic acid / glycol copolymers sold under the tradenames Texcare, Repel-o-tex, Gerol, Marloquest, Cirrasol.
  • the liquid detergent composition may optionally include a hydrotrope, which can prevent liquid crystal formation.
  • a hydrotrope which can prevent liquid crystal formation.
  • the addition of the hydrotrope thus aids the clarity/transparency of the composition.
  • Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate.
  • Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Salts of sulphonates can also be considered as anionic surfactants as defined herein.
  • the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance.
  • the amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
  • Enzymes can also be present in the formulation.
  • Preferred enzymes include protease, lipase, pectate lyase, amylase, cutinase, cellulase, mannanase. If present the enzymes may be stabilized with a known enzyme stabilizer for example boric acid.
  • Water, fluorescer and hydrotropes are mixed together at ambient temperature (approximately 22°C) for 2-3 minutes at a shear rate of 130 rpm using a Janke & Kunkel IKA RW20 overhead mixer. Salts and alkalis are added and mixed for 5 minutes prior to addition of surfactants and any alkyl ether carboxylic acid and/or fatty acid. The temperature of the mix rises to around 50-60°C at this point. After allowing to cool to ⁇ 30C, the LR400 solution, PVP or PVP/PVI and any remaining components such as perfume, preservatives, opacifier and dyes are added.
  • Formulations in accordance with the invention are listed in tables 1 & 2 Table 1
  • Comparative examples (A) & (B) include additional fatty acid at ca. 3 wt.% and 6 wt.% and demonstrate the disclosure of WO10/072628 A1 which disclosed formulations that include nonionic and anionic surfactants, fatty acid and cationic polymer.
  • Examples according to the invention (1) to (4) incorporate 2 different alkyl ether carboxylic acids (Emulsogen COL 080 and Marlowet 1072) at 2 different inclusion levels (3.3 and 6.6 wt.%).
  • the comparative examples A, & B and examples 1-4 were formulated to 3 different pH levels (pH 7, pH 7.5 and pH 8). The samples made at these various pH levels were stored overnight at 5°C. The formulation was deemed unstable if it had turned opaque, or if it has a significant haze that could not be seen through. The formulation was deemed stable if it was still clear. The results are shown in table 4: Table 4 Formulation pH 7 pH 7.5 pH 8 A Unstable Unstable Unstable Unstable B Unstable Unstable Unstable 1 Stable Stable Stable Stable 2 Stable Stable Stable 3 Stable Stable Stable Stable Stable Stable Stable Stable Stable Stable
  • formulations comprising alkyl ether carboxylic acids had a superior stability at low pH (pH 7 to 8.5) in comparison to the prior art formulations from WO10/072628 A1 which just included fatty acid.

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)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (11)

  1. Composition détergente liquide pour le linge comprenant :
    (a) de 2 à 40 % en poids de tensioactif non ionique, comprenant un éthoxylate d'alcool ;
    (b) de 4 à 40 % en poids de tensioactif anionique ;
    (c) de 1 à 12 % en poids d'acide carboxylique d'éther d'alkyle ou d'un sel carboxylate de celui-ci ; et
    (d) de 0,1 à 1,5 % en poids de polymère de polysaccharide cationique ; et
    (e) de 0,0001 à 0,01 % en poids d'un colorant de nuançage.
  2. Composition selon la revendication 1, ayant un pH de 6,2 à 9, de préférence de pH 6,5 à 8,5, plus préférablement de pH 6,5 à 8.
  3. Composition selon la revendication 1 ou la revendication 2, dans laquelle l'acide carboxylique d'éther d'alkyle ou le sel carboxylate de celui-ci est présent à raison de 1 à 10 % en poids, de préférence à raison de 2 à 7,5 % en poids.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'acide carboxylique d'éther d'alkyle ou le sel carboxylate est illustré par :
    Figure imgb0005
     formule dans laquelle R désigne une chaîne alkyle en C6 à C22 saturée ou insaturée ; soit R1 et R2 représentent tous deux un atome d'hydrogène ; soit R1 représente un atome d'hydrogène et R2 représente un groupe CH3 ; soit R1 représente un groupe CH3 et R2 représente un atome d'hydrogène ; R3 représente un atome d'hydrogène, ou un cation solubilisant tel que le sodium, le potassium, l'ammonium ou un ammonium substitué ; et n représente un nombre de 2 à 20, de préférence de 3 à 12, désignant le nombre de motifs répétitifs.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'acide carboxylique d'éther d'alkyle ou le sel carboxylate comporte une chaîne alkyle en C8 à C18 comportant entre 2 et 12 motifs répétitifs de glycol, dans laquelle les motifs répétitifs de glycol sont choisis parmi l'éthylène glycol, le propylène glycol ou des mélanges de ceux-ci.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère de polysaccharide cationique est présent à raison de 0,1 à 1 % en poids.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère de polysaccharide cationique est un polymère de cellulose cationique.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère de polysaccharide cationique est un polymère de guar cationique.
  9. Composition selon la revendication 7, dans laquelle le polymère de cellulose cationique est de l'hydroxy-éthylcellulose quaternisée.
  10. Composition selon l'une quelconque des revendications précédentes, laquelle composition comprend en outre un tensioactif de bétaïne.
  11. Composition selon l'une quelconque des revendications précédentes, laquelle composition comprend en outre un ingrédient choisi parmi un colorant de nuançage, une enzyme, un polymère antiredéposition, un polymère inhibant le transfert de colorant, un adjuvant, un séquestrant, un écran solaire et/ou un polymère permettant l'élimination des salissures.
EP12781306.1A 2011-12-12 2012-10-31 Compositions pour lessiver Active EP2791308B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12781306.1A EP2791308B1 (fr) 2011-12-12 2012-10-31 Compositions pour lessiver

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11192980 2011-12-12
EP12781306.1A EP2791308B1 (fr) 2011-12-12 2012-10-31 Compositions pour lessiver
PCT/EP2012/071590 WO2013087287A1 (fr) 2011-12-12 2012-10-31 Compositions pour lessiver

Publications (2)

Publication Number Publication Date
EP2791308A1 EP2791308A1 (fr) 2014-10-22
EP2791308B1 true EP2791308B1 (fr) 2015-12-16

Family

ID=47080545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12781306.1A Active EP2791308B1 (fr) 2011-12-12 2012-10-31 Compositions pour lessiver

Country Status (7)

Country Link
EP (1) EP2791308B1 (fr)
CN (1) CN103975049A (fr)
AR (1) AR089147A1 (fr)
BR (1) BR112014013668B1 (fr)
ES (1) ES2565528T3 (fr)
WO (2) WO2013087287A1 (fr)
ZA (1) ZA201403695B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779157A (zh) * 2014-12-24 2016-07-20 阎珊珊 一种薰衣草型洗衣液的制备
EP3472293B1 (fr) 2016-06-16 2022-03-30 Henkel AG & Co. KGaA Détergent à lessive liquide concentré à ph constant

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3101102B2 (fr) * 2015-06-05 2023-12-13 The Procter & Gamble Company Composition de detergent liquide compacte pour blanchisserie
US9828571B2 (en) 2015-06-05 2017-11-28 Illinois Tool Works, Inc. Heavy duty laundry detergent
EP3307861B1 (fr) 2015-06-11 2019-04-03 Unilever PLC, a company registered in England and Wales under company no. 41424 of Composition de détergent pour lessive
TR201906929T4 (tr) 2015-06-11 2019-05-21 Unilever Nv Çamaşır için deterjan bileşimi.
EP3433346B1 (fr) * 2016-03-21 2020-12-30 Unilever PLC Composition de détergent pour lessive
WO2017174251A1 (fr) * 2016-04-08 2017-10-12 Unilever Plc Composition de détergent à lessive
EP3440170B1 (fr) * 2016-04-08 2020-04-08 Unilever PLC Composition de détergent pour lessive
WO2018108382A1 (fr) * 2016-12-15 2018-06-21 Unilever Plc Composition détergente à lessive
EP3401384A1 (fr) * 2017-05-10 2018-11-14 Unilever PLC Composition détergente liquide pour le lavage
US11021383B2 (en) 2017-08-30 2021-06-01 Ecolab Usa Inc. Use of di-ionic compounds as corrosion inhibitors in a water system
PL240341B1 (pl) * 2018-03-20 2022-03-21 Przed Polaktiv Spolka Z Ograniczona Odpowiedzialnoscia Sposób prania tekstyliów bawełnianych i mieszankowych w pralnico-wirówce
CN111971372B (zh) * 2018-04-03 2022-03-11 联合利华知识产权控股有限公司 染料颗粒
AU2019331448B2 (en) 2018-08-29 2022-09-29 Ecolab Usa Inc. Use of multiple charged cationic compounds derived from primary amines or polyamines for microbial fouling control in a water system
US11084974B2 (en) 2018-08-29 2021-08-10 Championx Usa Inc. Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations
CA3110365C (fr) 2018-08-29 2023-05-09 Ecolab Usa Inc. Utilisation de composes ioniques a charges multiples derives de polyamines pour clarification d'eaux usees
CN112584910B (zh) 2018-08-29 2023-03-14 埃科莱布美国股份有限公司 衍生自多胺的带多个电荷的离子化合物及其组合物和其作为反相破乳剂用于油气操作的用途
CA3177148A1 (fr) 2018-08-29 2020-03-05 Ecolab Usa Inc. Composes ioniques a charges multiples derives de polyamines et compositions a base de ces composes et procedes de preparation associes
JP2020084023A (ja) * 2018-11-26 2020-06-04 花王株式会社 衣料用液体洗剤製品
EP3897143A1 (fr) 2019-01-29 2021-10-27 Ecolab USA Inc. Utilisation de composés cationiques à base de sucre pour lutter contre l'encrassement microbien dans un réseau d'alimentation en eau
CA3128188C (fr) 2019-01-29 2023-10-17 Ecolab Usa Inc. Utilisation de composes cationiques a base de sucre comme inhibiteurs de corrosion dans un reseau d'alimentation en eau
CN113840945B (zh) 2019-04-16 2023-09-26 埃科莱布美国股份有限公司 衍生自多胺的带多个电荷的阳离子化合物及其组合物用于水系统中的腐蚀抑制的用途
CN110452779A (zh) * 2019-09-11 2019-11-15 郑州华核新材料科技有限公司 纺织品表面黏着性沾染核素去污剂及其制备方法
CN110964605B (zh) * 2019-12-05 2022-06-28 广州立白企业集团有限公司 一种柔软型液体洗涤剂组合物

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR76189B (fr) 1981-07-13 1984-08-03 Procter & Gamble
GB8803036D0 (en) 1988-02-10 1988-03-09 Unilever Plc Liquid detergents
ES2107797T3 (es) * 1992-11-30 1997-12-01 Procter & Gamble Composiciones detergentes de alta formacion de espuma con jabones especialmente seleccionados.
DE4409189C2 (de) * 1994-03-17 1996-08-14 Chem Y Tensid-Zusammensetzung, insbesondere zur Verwendung in Körperreinigungsmitteln
GB9613941D0 (en) * 1996-07-03 1996-09-04 Procter & Gamble Cleansing compositions
DE102004048752A1 (de) * 2004-10-05 2006-04-06 Cognis Ip Management Gmbh Flüssige Tensidmischungen
DE102004051011A1 (de) * 2004-10-20 2005-06-23 Clariant Gmbh Flüssigwaschmittel enthaltend sekundäres Alkansulfonat und Farbfixiermittel
DE102004051714A1 (de) * 2004-10-23 2005-07-07 Clariant Gmbh Anionische Flüssigwaschmittel mit Farbfixiermitteln
EP2366009B1 (fr) * 2008-12-22 2012-10-24 Unilever PLC Compositions pour lessive

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105779157A (zh) * 2014-12-24 2016-07-20 阎珊珊 一种薰衣草型洗衣液的制备
EP3472293B1 (fr) 2016-06-16 2022-03-30 Henkel AG & Co. KGaA Détergent à lessive liquide concentré à ph constant

Also Published As

Publication number Publication date
BR112014013668B1 (pt) 2022-05-10
AR089147A1 (es) 2014-07-30
BR112014013668A2 (pt) 2017-06-13
ES2565528T3 (es) 2016-04-05
EP2791308A1 (fr) 2014-10-22
ZA201403695B (en) 2015-09-30
WO2013087284A1 (fr) 2013-06-20
WO2013087287A1 (fr) 2013-06-20
CN103975049A (zh) 2014-08-06

Similar Documents

Publication Publication Date Title
EP2791308B1 (fr) Compositions pour lessiver
EP2791310B1 (fr) Compositions de lavage
EP2922936B1 (fr) Compositions de lavage
EP3074495B1 (fr) Composition de blanchisserie
EP2909295B1 (fr) Compositions détergentes pour le linge
EP3074496B1 (fr) Compositions pour la lessive
EP3074497B1 (fr) Compositions de lavage
EP2366008B1 (fr) Compositions de lessive
WO2013087285A1 (fr) Compositions pour lessiver et utilisations
EP2366009B1 (fr) Compositions pour lessive
EP2922938B1 (fr) Compositions de lavage
CN107075422B (zh) 洗衣组合物成分
EP2922937B1 (fr) Ingrédient pour utilisation dans une composition de blanchissage
WO2016066369A1 (fr) Réduction de la détérioration des couleurs pendant le procédé de lavage du linge

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: 20140603

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/29 20060101ALI20150616BHEP

Ipc: C11D 3/37 20060101ALI20150616BHEP

Ipc: C11D 1/72 20060101ALI20150616BHEP

Ipc: C11D 1/06 20060101ALI20150616BHEP

Ipc: C11D 1/83 20060101AFI20150616BHEP

Ipc: C11D 3/22 20060101ALI20150616BHEP

Ipc: C11D 3/00 20060101ALI20150616BHEP

Ipc: C11D 1/22 20060101ALI20150616BHEP

INTG Intention to grant announced

Effective date: 20150714

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

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 765570

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012013212

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2565528

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160405

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20151216

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: 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: 20160316

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: 20151216

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: 20151216

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 765570

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151216

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

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: 20151216

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: 20151216

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: 20151216

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: 20151216

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: 20160317

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: 20151216

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

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: 20151216

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: 20151216

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: 20151216

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: 20151216

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: 20151216

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: 20160418

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: 20151216

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: 20160416

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012013212

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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: 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: 20151216

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: 20151216

26N No opposition filed

Effective date: 20160919

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: 20151216

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: 20151216

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

Ref country code: ES

Payment date: 20161011

Year of fee payment: 5

Ref country code: IT

Payment date: 20161024

Year of fee payment: 5

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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: 20161031

Ref country code: CH

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

Effective date: 20161031

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: 20161031

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

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: 20161031

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: 20121031

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: 20151216

Ref country code: MT

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

Effective date: 20161031

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: 20151216

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: 20151216

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

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: 20151216

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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: 20151216

Ref country code: IT

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

Effective date: 20171031

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181221

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: 20171101

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602012013212

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER N.V., ROTTERDAM, NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

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

Effective date: 20230428

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

Ref country code: GB

Payment date: 20231020

Year of fee payment: 12

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

Ref country code: TR

Payment date: 20231030

Year of fee payment: 12

Ref country code: FR

Payment date: 20231025

Year of fee payment: 12

Ref country code: DE

Payment date: 20231020

Year of fee payment: 12