[go: up one dir, main page]

EP2850166B1 - Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé - Google Patents

Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé Download PDF

Info

Publication number
EP2850166B1
EP2850166B1 EP13723106.4A EP13723106A EP2850166B1 EP 2850166 B1 EP2850166 B1 EP 2850166B1 EP 13723106 A EP13723106 A EP 13723106A EP 2850166 B1 EP2850166 B1 EP 2850166B1
Authority
EP
European Patent Office
Prior art keywords
composition according
pei
polymer
polyalkoxyl
chain
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
EP13723106.4A
Other languages
German (de)
English (en)
Other versions
EP2850166A1 (fr
Inventor
Stephen Norman Batchelor
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 EP13723106.4A priority Critical patent/EP2850166B1/fr
Publication of EP2850166A1 publication Critical patent/EP2850166A1/fr
Application granted granted Critical
Publication of EP2850166B1 publication Critical patent/EP2850166B1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • This invention relates to laundry detergent compositions comprising an alkoxylated polyethyleneimine anti-redeposition polymer (ARP) and detergency surfactants, particularly anionic and nonionic detergency surfactants.
  • ARP alkoxylated polyethyleneimine anti-redeposition polymer
  • Ethoxylated PEI polyethylene imine
  • the PEI(600)20EO material with all primary and secondary amino groups fully substituted by EO 20 polyalkoxylation is not a good ARP for laundry detergents.
  • These alkoxylated PEIs are usually formed by direct reaction of ethylene oxide, and/or propylene oxide, and PEI as described in CA 1210009 .
  • EP 2050792 discloses the preparation of a PEI plus tosylated PEG monomethyl ether as an intermediate in the preparation of a PEG-PEI-epoxy resin structure. This preparation is repeated in EP 2147733 .
  • JP 2007/099929 (Dainippon Ink & Chem.) also discloses the addition of tosylated PEG monomethyl ether to PEI followed by the addition of a styrene monomer.
  • the molar ratio of mPEG to PEI used is at least 3:1 which should give an average of at least 3 polyalkoxyl chains attached to each PEI.
  • Zhang & Lonnie Chen & Lonnie (Chinese J. Chem., Vol 21 p 460-5, 2003 ) discusses the preparation of PEI-PEO block copolymers and their clay dispersancy.
  • the polymers are triblock polymers formed from divalently modified PEG (dimesyl). This forms a PEO crosslink between two PEI groups. Such crosslinked PEI is not desirable due to its lower weight efficiency.
  • Non-ionic containing formulations are widely used in laundry, especially for low suds formulations suitable for front loading automatic washing machines.
  • PEI tends to deposit soil onto nylon elastane based fabrics. EPEI does not suffer from the same nylon- elastane negatives as PEI and has consequently been widely used in laundry compositions. However, it would be desirable to improve the performance of EPEI as a soil suspending polymer to solve the problem of redeposition over the full range of fabrics found in a typical laundry load: cotton, polycotton, polyester and nylon-elastane.
  • a laundry detergent composition containing 5 to 30 wt% detersive surfactant selected from non-ionic and anionic surfactant and 0.05 to 4 wt%, preferably 0.1 to 2 wt%, of polyalkoxylated polyethylene imine polymer wherein the polymer is a PEI which has a molar ratio of polyalkoxyl chains to PEI of less than or equal to 3 resulting in 3 or fewer nitrogens, preferably 2 or fewer nitrogens, most preferably 1 nitrogen, bound to polyalkoxyl chains and wherein the PEI has a Mw of at least 500, preferably 1000 to 2000, more preferably less than 1500 and even about 1300. Mw is the weight average molecular weight The molecular weights are preferably determined by dynamic light scattering using a Zetasizer Nano (Malvern).
  • fraction of (wt% non-ionic)/(wt% anionic surfactant) is from 0.6 to 2.0, preferably from 0.90 to 1.2.
  • composition according to the first aspect is diluted to a level of 0.3 to 1g/L surfactant and 5 to 150 ppm, preferably 10 to 80 ppm polymer according to the first aspect and used to launder fabrics.
  • Each polyalkoxyl chain is preferably built from ethoxy and/or propoxy groups. Most preferably it is a polyethoxyl chain. Preferably the polyalkoxyl chain contains 5 to 60 alkoxyl repeat units, more preferably 8 to 20, most preferably 10 to 14. Chains may be alkyl capped, preferably methyl capped. To facilitate the bonding of the capped polyalkoxyl chain with the PEI the chain is preferably provided with a reactive group at the end to be linked to the PEI.
  • Suitable reactive groups may be selected from epoxides, alkenes, a sulfooxyethylsulfonyl reactive group (-SO 2 CH 2 CH 2 OSO 3 Na), heterocyclic reactive groups and leaving groups such as tosylate.
  • the heterocyclic reactive groups are preferably nitrogen containing aromatic rings bound to a halogen or an ammonium group, which react with NH 2 or NH groups to form a covalent bond.
  • the preformed alkoxy chain contains only 1 reactive group, the other chain end is typically alkyl capped. Each chain has a terminal group with molecular weight less than 100.
  • the terminal group on the polyalkoxyl chain may be a C 1-4 alkyl group, preferably a methyl group.
  • the detergent compositions may take any suitable form.
  • they may be powders, tablets, liquids or gels and in the case of liquids they may be contained in a water soluble capsule to allow for ease of use.
  • Preferred compositions are liquids due to the compatibility of the polyalkoxylated PEI ARP materials with ingredients typically found in liquid detergents.
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • Blends of anionic and nonionic surfactants are a preferred feature of the compositions.
  • the amount of anionic surfactant is preferably at least 5 wt%, more preferably at least 10wt%.
  • Preferred anionic surfactants are alkyl sulphonates especially alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 .
  • the counter ion for the anionic surfactants is may be an alkali metal, typically sodium, or another counter-ion for example MEA, TEA or ammonium can be used.
  • Suitable linear alkyl benzene sulphonate surfactants include Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14.
  • composition comprises an alkyl polyethoxylate sulphate anionic surfactant of the formula (II): RO(C 2 H 4 O) x SO 3 - M + (II) where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated
  • M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • R is an alkyl chain having from 12 to 16 carbon atoms
  • M is Sodium and x averages from 1 to 3, preferably x is 3;
  • SLES sodium lauryl ether sulphate
  • It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C 12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.
  • Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
  • the composition contains from 0.1 to 20 wt% preferably 1 wt% to 15 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
  • a non-ionic surfactant for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
  • glucamides N
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • composition may comprise up to 10 wt% of an amine oxide of the formula (III): R 1 N(O)(CH 2 R 2 ) 2 (III)
  • R 1 is a long chain moiety each CH 2 R 2 are short chain moieties.
  • R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • Preferred amine oxides have R 1 is C 8 -C 18 alkyl, and R 2 is H. These amine oxides are illustrated by C 12 - 14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman under the trade name Empigen® OB.
  • Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R 2 is H
  • R 2 may be CH 2 OH, for example: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
  • Preferred amine oxides have the formula (IV): O - - N + (Me) 2 R 1 (IV) where R 1 is C 12-16 alkyl, preferably C 12-14 alkyl; Me is a methyl group.
  • a preferred zwitterionic material is a carbobetaine available from Huntsman under the name Empigen® BB. Betaines and / or amine oxides, improve particulate soil detergency in the compositions.
  • surfactants than the preferred LAS, SLES, nonionic and amine oxide/ carbobetaine may be added to the mixture of detersive surfactants.
  • cationic surfactants are preferably substantially absent.
  • alkyl sulphate surfactant may be used, especially the non-ethoxylated C 12-15 primary and secondary alkyl sulphates.
  • compositions may include 0.5 wt% or more of a soil release polymer which is substantive to polyester fabric.
  • a soil release polymer which is substantive to polyester fabric.
  • Such polymers typically have a fabric substantive midblock formed from propylene terephthalate repeat units and one or two end blocks of capped polyalkylene oxide, typically PEG 750 to 2000 with methyl end capping.
  • polyester soil release polymer there may be used dye transfer inhibition polymers, and cotton soil release polymers, especially those based on modified cellulosic materials.
  • a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic.
  • suitable hydrotropes there may be mentioned as preferred: MPG (monopropylene glycol), glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • At least one or more enzymes may be present in the compositions.
  • at least two, more preferably at least three different classes of enzymes are used in combination.
  • Preferred enzyme cocktails are selected from the group comprising: lipase, Phospholipase, protease, Cutinase, Amylase, Cellulase, Peroxidases/oxidase, Pectate Lyase, and Mannanase.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • the enzymes may be protected by encapsulation.
  • a lignin compound may be used in the composition.
  • the lignin compound comprises a lignin polymer and more preferably it is a modified lignin polymer.
  • a modified lignin polymer as used herein is lignin that has been subjected to a chemical reaction to attach chemical moieties to the lignin covalently. The attached chemical moieties are preferably randomly substituted.
  • fluorescer in the compositions.
  • 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 0.5 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. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • DI-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluoroscers are: sodium 2 (4-styry)-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anillino-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.
  • Compositions may comprise a weight efficient bleach system. Such systems typically do not utilise the conventional percarbonate and bleach activator approach.
  • An air bleach catalyst system is preferred.
  • Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098 ; WO 98/39406 , WO 97/48787 , WO 00/29537 ; WO 00/52124 , and WO00/60045 .
  • An example of a preferred catalyst is a transition metal complex of MeN4 Py ligand (N,N- bis(pyridin-2-yl-metyl)-1,1-bis (pyridin-2-yl)-1 aminoethane).
  • Suitable bispidon catalyst materials and their action are described in WO 02/48301 .
  • the bleach catalyst may be encapsulated to reduce interaction with other components of the liquid during storage.
  • Photobleaches may also be employed.
  • a "photobleach” is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction.
  • Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches.
  • Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
  • the phthalocyanin has 1-4 SO 3 X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba).
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10 wt%, preferably about 0.001 to about 5 wt%.
  • composition will normally include one of more perfume components. Free oil and encapsulated perfumes may be used, and mixtures thereof.
  • a particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume.
  • Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
  • the perfume is not only encapsulated but also that the encapsulated perfume is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics.
  • the deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption.
  • compositions may contain one or more other ingredients.
  • ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
  • the compositions may further comprise colorants, pearlisers and/or opacifiers, and shading dye.
  • Shading dye can be used to improve the performance of the compositions.
  • Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
  • a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself. Examples of shading dyes are alkoxylated thiophene dyes, acid violet 50, direct violet 35, direct violet 99, direct violet 9, solvent violet 13, disperse violet 28, disperse blue 165.
  • Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer.
  • 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, and citric acid.
  • DEQUESTTM 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, for example those sold by BASF under the name SOKALANTM.
  • the organic 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.
  • a preferred sequestrant is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid), for example sold as Dequest 2010. Also suitable but less preferred as it gives inferior cleaning results is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • buffers are MEA, and TEA. If present they are preferably used in the composition at levels of from 1 to 15 wt%.
  • compositions may have their rheology modified by use of a material or materials that form a structuring network within the composition.
  • Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants for example citrus pulp fibre. Citrus pulp fibre is particularly preferred especially if lipase enzyme is included in the composition.
  • compositions may comprise visual cues of solid material that is not dissolved in the composition.
  • visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid.
  • Enzymes and bleach catalysts are examples of such ingredients.
  • perfume, particularly microencapsulated perfume are examples of such ingredients.
  • Tosyl chloride was added, over 45 min, to a stirred mixture of poly(ethylene glycol) methyl ether and triethylamine in dichloromethane at 0 to 5°C. The mixture was then allowed to warm to ambient temperature and was stirred at room temperature for 16 hr. after which essentially all of the tosyl chloride had been consumed, as judged by thin layer chromatography. The reaction yielded a suspension (192 g) of Tosylated PEG.
  • the molar ratio of Tosylated PEG to Polyethyleneimine was 1:1.
  • the mixture was stirred overnight (16 hr) at room temperature, after which the formation of para-toluene sulphonic acid was completed as measured by TLC, the pH was then adjusted to 7.0 with conc. hydrochloric acid and bottled.
  • the synthesis was repeated with different molar ratios of Tosylated PEG to Polyethyleneimine to give a series of polymers as detailed in Table 1.
  • P10 and P30 are labelled comparative because they resemble the alkoxylated polyethylene imines of the prior art.
  • Table 1 Polymer Code Molar ratio Tosylated PEG:Polyethyleneimine P1 1:1 P2 2:1 P3 3:1 P10 (reference) 10:1 P30 (reference) 30:1
  • the base laundry detergent composition used for wash testing is given in Table 2.
  • Table 2 wt% (solids) NaLAS 4.9 NI(7EO) 7.3 SLES(3EO) 2.4 Alkyl Betaine 0.9 1,2-propanediol 15.0 Triethanolamine 2.0 Free oil perfume 1.4 Water to 100
  • the composition was used to wash a mixture of white fabrics: woven cotton, micro-fibre polyester, woven polycotton and knitted nylon-elastane with a liquor to cloth ratio of 10:1 in a Linitester.
  • the fabrics were of equal area. 26° French Hard water was used. Each wash lasted 20 minutes and was followed by 2 rinses in 75 ml water. This procedure was repeated twice in the base composition given in Table 2 (i.e. without any polymer) and then the fabric was then dried.
  • the wash procedure was then repeated three more times, now with the addition of soil strips to each wash to simulate soiling.
  • the weight ratio of soil strips to the white fabrics was 8.6:1.
  • the soil strips used were SBL 2004 Soil Ballast Fabrics (ex wfk Testgewebe GmbH) and a Stanley Clay strip (ex Warwick Equest UK) in the weight ratio of 1:1.
  • 3.5 wt% of polymer was also included in the composition - the water balance being correspondingly reduced.
  • the compositions were all used at 2.3 g/L.
  • the polymers P1 (with 1 ethoxylated chain) and P2 (with 2 ethoxylated chains) show the best performance overall performance, with good effects on cotton, polycotton and polyester, without a large negative on nylon-elastane as seen from the totally unalkoxylated PEI.
  • P1, P1-750 and P1-2000 provided improved results over the P30 and the PEI(1300) reference polymer.
  • the shorter chain alkoxylated PEI provided the best results.
  • the polymers of the invention provide benefits at low levels.
  • Table 7 is a further detergent composition according to the invention.
  • Table 7 wt% (solids) NaLAS 4.9 NI(7EO) 7.3 SLES(3EO) 2.4 Alkyl Betaine 0.9 1,2-propanediol 15.0 Triethanolamine 2.0 Free oil perfume 1.4 P1 0.3 Lipase 0.002 Cellulase 0.002 Amylase 0.002 Acid Violet 50 0.002 Fluorescer 0.1 Water to 100
  • Enzyme levels are expressed as pure protein.
  • the lipase used was LipocleanTM (Novozymes); the cellulose used was CellucleanTM (Novozymes); the amylase used was StainzymeTM (Novozymes).

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)
  • Detergent Compositions (AREA)

Claims (11)

  1. Composition détergente pour le linge contenant 5 à 30 % en poids de tensloactif détersif choisi parmi les tensioactifs non-ioniques et anioniques et 0,05 à 4 % en poids d'un polymère de polyéthylène-imine polyalcoxylée dont les chaînes polyalcoxy sont directement liées aux azotes dans la PEI et chaque chaîne a un groupe terminal ayant une masse moléculaire inférieure à 100, et dans laquelle le polymère est une PEI qui a un rapport molaire des chaînes polyalcoxy, y compris le groupe terminal, à la PEI, inférieur ou égal à 3, ayant pour résultat 3 ou moins, de préférence 2 ou moins, tout spécialement 1, azotes liés à des chaînes polyalcoxy, et dans laquelle la PEI a une Mw d'au moins 500, de préférence de 1000 à 2000, mieux encore inférieure à 1500 et même d'environ 1300.
  2. Composition selon la revendication 1, dans laquelle la fraction (% en poids de tensioactif non-ionique)/(% en poids de tensioactif anionique) est de 0,6 à 2,0.
  3. Composition selon la revendication 2, dans laquelle la fraction (% en poids de tensioactif non-ionique)/(% en poids de tensioactif anionique) est de 0,90 à 1,2.
  4. Composition selon l'une quelconque des revendications précédentes, qui est un liquide.
  5. Composition selon l'une quelconque des revendications 1 à 3, qui est un solide.
  6. Composition selon l'une quelconque des revendications précédentes, comprenant en outre un parfum.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle le groupe terminal sur la chaîne polyalcoxy est un groupe alkyle en Ci à C4, de préférence un groupe méthyle.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle la polyalcoxylation consiste en une polyéthoxylation.
  9. Composition selon la revendication 8, dans laquelle le nombre moyen de motifs oxyde d'éthylène dans la PEI polyéthoxylée est de 5 à 50, de préférence de 8 à 20, mieux encore de 10 à 14.
  10. Composition selon l'une quelconque des revendications précédentes, comprenant un tensioactif non-ionique éthoxylé.
  11. Procédé de lavage du linge dans lequel une composition selon l'une quelconque des revendications 1 à 10 est diluée à un niveau de 0,3 à 1 g/l de tensioactif détersif et de 5 à 150 ppm, de préférence de 10 à 80 ppm de polymère de polyéthylène-imine polyalcoxylée et est utilisée pour laver une charge mixte de tissus comprenant du nylon-élastane et au moins un autre tissu choisi dans le groupe comprenant le coton, le polycoton et le polyester.
EP13723106.4A 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé Active EP2850166B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13723106.4A EP2850166B1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP12168345 2012-05-16
EP13152414 2013-01-23
PCT/EP2013/059939 WO2013171210A1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé
EP13723106.4A EP2850166B1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Publications (2)

Publication Number Publication Date
EP2850166A1 EP2850166A1 (fr) 2015-03-25
EP2850166B1 true EP2850166B1 (fr) 2015-10-21

Family

ID=48446329

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13723106.4A Active EP2850166B1 (fr) 2012-05-16 2013-05-14 Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé

Country Status (7)

Country Link
EP (1) EP2850166B1 (fr)
CN (1) CN104334707B (fr)
BR (1) BR112014026932B1 (fr)
ES (1) ES2556490T3 (fr)
IN (1) IN2014MN02280A (fr)
WO (1) WO2013171210A1 (fr)
ZA (1) ZA201407332B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4663735A1 (fr) * 2024-06-10 2025-12-17 Henkel AG & Co. KGaA Composition détergente pour renforcer la structure textile

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112016005223B1 (pt) 2013-09-17 2021-10-13 Unilever Ip Holdings B.V. Polímero corante azul ou violeta, composição para lavagem de roupa e método doméstico de tratamento de um têxtil
CA2974862C (fr) * 2015-02-13 2023-07-25 Unilever Plc Composition de liquide de lessive comprenant un melange d'agents de surface anioniques et non ioniques et de polymeres de teintage
CN107207997A (zh) * 2015-02-13 2017-09-26 荷兰联合利华有限公司 液体洗衣组合物
BR112017016809A2 (pt) * 2015-02-13 2018-04-03 Unilever Nv formulação de detergente líquido para a lavagem de roupas e método caseiro para lavagem de roupas
WO2019038187A1 (fr) * 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
CN112243455B (zh) * 2018-06-26 2022-04-29 宝洁公司 液体衣物洗涤剂组合物
EP3983511B1 (fr) 2019-06-14 2023-07-12 Dow Global Technologies LLC Formulation détergente pour lessive liquide
DE102020212091A1 (de) * 2020-09-25 2022-03-31 Henkel Ag & Co. Kgaa Konzentrierte fließfähige Waschmittelzubereitung mit verbesserten Eigenschaften

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1210009A (fr) 1982-12-23 1986-08-19 Eugene P. Gosselink Polymeres d'amines ethoxyles possedant des proprietes d'elimination de sol argileux, et d'antiredeposition, utiles dans des compositions detergentes
EP0511456A1 (fr) 1991-04-30 1992-11-04 The Procter & Gamble Company Détergents liquides contenant un ester aromatique de l'acide borique pour inhibition d'enzyme protéolitique
SK120893A3 (en) 1991-04-30 1994-08-10 Procter & Gamble Liquid detergent mixtures with boric-polyol complex for inhibition of proteolytic enzyme
US6310025B1 (en) * 1996-03-04 2001-10-30 The Procter & Gamble Company Laundry pretreatment process and bleaching compositions
AU2892897A (en) 1996-06-19 1998-01-07 Unilever Plc Bleach activation
ZA981883B (en) 1997-03-07 1998-09-01 Univ Kansas Catalysts and methods for catalytic oxidation
ATE295408T1 (de) 1997-03-07 2005-05-15 Procter & Gamble Bleichmittelzusammensetzungen
WO2000029537A1 (fr) 1998-11-13 2000-05-25 The Procter & Gamble Company Compositions de blanchiment
CZ20013157A3 (cs) 1999-03-02 2002-07-17 The Procter & Gamble Company Pouľití makropolycyklického ligandu s příčnými můstky, bělící prostředek, tekutý prací, prací namáčecí nebo předpírací prostředek, způsob pro bělení ąpinavých a potřísněných textilií
AU4061900A (en) 1999-04-01 2000-10-23 Procter & Gamble Company, The Transition metal bleaching agents
GB0030673D0 (en) 2000-12-15 2001-01-31 Unilever Plc Ligand and complex for catalytically bleaching a substrate
PL1651745T3 (pl) 2003-08-06 2007-07-31 Ciba Specialty Chemicals Holding Inc Kompozycja podbarwiająca
EP1869151A2 (fr) * 2005-04-15 2007-12-26 The Procter and Gamble Company Compositions detergentes liquides a stabilite et transparence ameliorees pour la lessive
JP4937996B2 (ja) * 2005-04-15 2012-05-23 ザ プロクター アンド ギャンブル カンパニー アルコキシル化ポリアルキレンイミン類を有する洗浄組成物
JP4979219B2 (ja) 2005-10-05 2012-07-18 Ｄｉｃ株式会社 親水性コロイド粒子及びその製造方法
EP2050792B1 (fr) 2006-08-09 2013-11-20 DIC Corporation Dispersion de nanoparticules métalliques et leur procédé de production
EP2147733A4 (fr) 2007-05-16 2012-12-12 Dainippon Ink & Chemicals Procédé de production de nanostructure contenant de l'argent, et nanostructure contenant de l'argent
WO2009060059A2 (fr) * 2007-11-09 2009-05-14 Basf Se Polyalkylèneimines alcoxylés amphiphiles solubles dans l'eau présentant un bloc interne d'oxyde de polyéthylène et un bloc externe d'oxyde de polypropylène
GB0810881D0 (en) * 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning
AU2010309968B2 (en) * 2009-10-23 2014-01-16 Unilever Global Ip Limited Dye polymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4663735A1 (fr) * 2024-06-10 2025-12-17 Henkel AG & Co. KGaA Composition détergente pour renforcer la structure textile

Also Published As

Publication number Publication date
ZA201407332B (en) 2016-05-25
ES2556490T3 (es) 2016-01-18
CN104334707B (zh) 2017-08-22
BR112014026932A2 (pt) 2017-06-27
EP2850166A1 (fr) 2015-03-25
IN2014MN02280A (fr) 2015-10-09
BR112014026932A8 (pt) 2021-04-13
WO2013171210A1 (fr) 2013-11-21
CN104334707A (zh) 2015-02-04
BR112014026932B1 (pt) 2021-08-31

Similar Documents

Publication Publication Date Title
EP2850166B1 (fr) Compositions détergentes de lessive comprenant un polyéthylène-imine polyalcoxylé
RU2469080C2 (ru) Чистящие композиции, содержащие амфифильные водорастворимые полиалкиленимины, имеющие внутренний полиэтиленоксидный блок и концевой полипропиленоксидный блок
US7205269B2 (en) Laundry detergent compositions with hueing dye
EP2880074B1 (fr) Compositions alcalines de détergent liquide pour la lessive comprenant des polyesters
EP3039112B1 (fr) Compositions de nettoyage contenant une polyétheramine
EP2978740B1 (fr) Polyétheramines sur la base de 1,3-dialcohols
EP2707472B1 (fr) Compositions de détergent de blanchisserie concentrées aqueuses
US20050288206A1 (en) Laundry detergent compositions with efficient hueing dye
EP4133042B1 (fr) Composition de détergent à lessive
US6462008B1 (en) Detergent compositions comprising photobleaching delivery systems
EP2522714A1 (fr) Compositions de détergent concentré aqueux pour le linge
EP3649224B1 (fr) Compositions de nettoyage comprenant des esteramines alcoxylées
EP2992073B1 (fr) Procédé pour épaissir une composition de détergent liquide
WO2016049387A1 (fr) Compositions de nettoyage contenant une polyétheramine
EP2948535B1 (fr) Matériau additif de lessive non coloré pour la promotion d'antiredéposition de particules de saleté
EP2770044A1 (fr) Gel lamellaire avec un oxyde d'amine
US10316273B2 (en) Thickened aqueous detergent liquid
CA2800522A1 (fr) Procede de fabrication d'une composition detergente liquide
WO2000052122A1 (fr) Compositions de detergent contenant des systemes d'apport d'agent de photoblanchiment
WO2017202923A1 (fr) Composition de blanchisserie
WO2017202922A1 (fr) Composition de lavage du linge
AU2013298728B9 (en) Alkaline liquid laundry detergent compositions comprising polyesters

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: 20141016

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

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
INTG Intention to grant announced

Effective date: 20150708

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

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: NL

Ref legal event code: MP

Effective date: 20151021

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: AT

Ref legal event code: REF

Ref document number: 756621

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151115

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: 602013003582

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2556490

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160118

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 756621

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151021

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

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: 20151021

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: 20160121

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: 20151021

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: 20151021

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: 20151021

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: 20160221

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

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

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: 20151021

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: 20160122

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: 20151021

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: 20151021

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: 20160222

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: 20151021

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: 20151021

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: 20151021

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013003582

Country of ref document: DE

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: 20151021

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: 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: 20151021

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: 20151021

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: 20151021

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: 20151021

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: 20151021

26N No opposition filed

Effective date: 20160722

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: 20151021

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: 20160514

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20160531

Ref country code: CH

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

Effective date: 20160531

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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: 20160514

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

Ref country code: BE

Payment date: 20170519

Year of fee payment: 5

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: 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: 20130514

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

Ref country code: MC

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

Effective date: 20151021

Ref country code: MT

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

Effective date: 20160531

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: 20151021

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: 20151021

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: 20151021

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: 20151021

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180531

Ref country code: BE

Ref legal event code: FP

Effective date: 20151201

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: 20180531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602013003582

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: ES

Ref legal event code: PC2A

Owner name: UNILEVER IP HOLDINGS B.V.

Effective date: 20211228

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: DE

Payment date: 20250521

Year of fee payment: 13

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

Ref country code: GB

Payment date: 20250521

Year of fee payment: 13

Ref country code: ES

Payment date: 20250627

Year of fee payment: 13

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

Ref country code: FR

Payment date: 20250528

Year of fee payment: 13

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

Ref country code: TR

Payment date: 20250506

Year of fee payment: 13