EP3074497B1 - Compositions de lavage - Google Patents

Compositions de lavage Download PDF

Info

Publication number
EP3074497B1
EP3074497B1 EP14805217.8A EP14805217A EP3074497B1 EP 3074497 B1 EP3074497 B1 EP 3074497B1 EP 14805217 A EP14805217 A EP 14805217A EP 3074497 B1 EP3074497 B1 EP 3074497B1
Authority
EP
European Patent Office
Prior art keywords
composition according
silicone
anionic
polymer
cationic
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
EP14805217.8A
Other languages
German (de)
English (en)
Other versions
EP3074497A1 (fr
Inventor
Andrew Anthony Howard Barnes
Martin Charles Crossman
Belinda Fay DAWSON
Paula Rose Bernadette GILFOYLE
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 EP14805217.8A priority Critical patent/EP3074497B1/fr
Publication of EP3074497A1 publication Critical patent/EP3074497A1/fr
Application granted granted Critical
Publication of EP3074497B1 publication Critical patent/EP3074497B1/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
    • C11D3/20—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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D3/50—Perfumes

Definitions

  • This invention relates to a laundry composition. More particularly, the invention is directed to a softening in the wash laundry composition.
  • Fabric softening silicones have been used to provide softness to fabrics from a laundry detergent composition. However, there is a problem with formulation stability in terms of unacceptable haze.
  • the invention is directed to a liquid laundry detergent composition
  • a liquid laundry detergent composition comprising:-
  • the anionic silicone has a molecular weight of from 1,000 to 100,000, more preferably from 2,000 to 50,000 even more preferably from 5,000 to 50,000, most preferably from 10,000 to 50,000.
  • the anionic silicone has an anionic group content of at least 1 mol%, preferably 2 mol%.
  • the anionic silicone comprises a carboxy silicone.
  • the silicone is added to the formulation in the form of an emulsion, more preferably in the form of a nonionic emulsion, most preferably using a branched nonionic emulsifier.
  • a preferred level of the anionic silicone is present at a level of from 0.1 to 2.5 wt.%, preferably from 0.1 to 2 wt.%.
  • the liquid detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9.5, most preferably from pH 7 to 9, for example from pH 7.5 to 8.5.
  • a preferred level of the cationic polymer is from 0.1 to 2 wt.%, more preferably from 0.1 to 1 wt.%, most preferably from 0.1 to 0.75 wt.%.
  • a preferred cationic cellulose polymer is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose).
  • the weight ratio of the silicone to the cationic polymer is from 5:1 to 1:1.
  • the composition further comprises an ingredient selected from, fatty acids or salts thereof, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen, and/or soil release polymer.
  • the invention provides the use of a composition according to the first aspect of the invention to soften fabrics.
  • the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
  • the invention is directed to laundry compositions containing surfactant, a cationic cellulose polymer having a specific nitrogen content, a fabric softening anionic silicone, a perfume, and a fluorescer.
  • the invention can take any of a number of forms that are liquid laundry compositions (such as gels and aqueous liquids). Preferably they are main wash products. It can take the form of a laundry composition for the main wash, which may be dilutable or non-dilutable.
  • the laundry composition may for example be an isotropic liquid, or a surfactant-structured liquid.
  • Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".
  • the liquid detergent composition has a pH of from 6 to 10, more preferably from pH 6.5 to 9.5, most preferably from pH 7 to 9, for example from pH 7.5 to 8.5.
  • the detergent composition preferably comprises both anionic surfactant and nonionic surfactant.
  • the weight ratio of anionic to nonionic surfactant is from 5:1 to 1:3. More preferably the weight ratio of anionic to nonionic surfactant is from 5:1 to 1:2, even more preferably from 5:1 to 1:1.25, most preferably from 5:1 to 1:1, for example from 4:1 to 1:1.
  • 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.
  • the alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide. Typically an aliphatic C 8 to C 18 primary or secondary linear or branched alcohol 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.
  • 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 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 total amount of surfactant present in the composition is from 5 to 40 wt.%.
  • the surfactant level is preferably at least 6 wt.%, more preferably at least 10 wt.%, More preferably the total amount of surfactant is from 12.5 to 40 wt.%, preferably from 15 to 35 wt.%.
  • a preferred surfactant system comprises anionic and nonionic surfactant.
  • the nonionic detergent is preferably present in amounts of from 2 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the nonionic component of the detergent is present from 20 to 75 wt.% more preferably 25 to 60 wt.% of the total surfactant content.
  • the nonionic surfactant preferably comprises alcohol ethoxylate.
  • a preferred nonionic surfactant is C 12 -C 15 alkyl chain with an average of 7 to 9 moles of ethoxylation.
  • the anionic surfactant is preferably present in amounts of from 4 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the anionic component of the detergent is present from 25 to 80 wt.%, more preferably 40 to 80 wt.%, most preferably from 50 to 80 wt.% of the total surfactant content.
  • Preferred anionic surfactants are: linear alkyl benezene sulphonates, sodium lauryl ether sulphonates with 1 to 3 moles (average) of ethoxylation, primary alkyl sulphonates, methyl ether sulphates and secondary alkyl sulphonates or mixtures thereof.
  • the anionic surfactant preferably comprises linear alkylbenzene sulfonate.
  • fatty acid and their salts are not included in the level of surfactant.
  • surfactants such as amphoteric, zwitterionic and cationic surfactants may also be present in addition to the aforementioned nonionic and anionic surfactants.
  • Silicones and their chemistry is described in, for example, The Encyclopedia of Polymer Science, volume 11, p765 .
  • the composition comprises fabric softening anionic silicone at a level of from 0.05 to 5 wt.%, preferably from 0.1 to 2.5 wt.%, more preferably from 0.1 to 2 wt.%.
  • fabric softening anionic silicone examples include silicones that incorporate carboxylic, sulphate, sulphonic, phosphate and/or phosphonate functionality.
  • Preferred anionic silicones are carboxyl functionalised silicones.
  • the anionic silicone may be in the form of the acid or the anion.
  • the carboxyl functionalised silicone it may be present as a carboxylic acid or carboxylate anion.
  • Examples of commercially available materials are:- X-22-3710, X-22-162C and X-22-3701 E from Shin Etsu; CSi 2342 and Tego polish R20 from Evonik; SFD 209 from Dow Corning; Silube CS-1, CP-1 Silphos J208 from Siltech; Pecosil PS-100, PS112, PS 11220, WDS 100 from Phoenix Chemical; and, Hansa LPF 711 from CHT Beitlich.
  • the anionic silicone has a molecular weight of from 1,000 to 100,000, more preferably from 2,000 to 50,000 even more preferably from 5,000 to 50,000, most preferably from 10,000 to 50,000.
  • the anionic silicone has an anionic group content of at least 1 mol%, preferably 2 mol%.
  • the silicone is added to the formulation in the form of an emulsion, more preferably in the form of a nonionic emulsion. More preferably the emulsion is prepared from nonionic emulsifiers, more preferably branched nonionic emulsifiers for examples Ecosurf EH-3 (Dow Chemical) or Berol 840 (Akzo Nobel).
  • the composition comprises a cationic cellulose polymer at a level of from 0.05 to 2.5 wt.%, preferably from 0.1 to 2 wt.%, more preferably from 0.1 to 1 wt.%, most preferably from 0.1 to 0.75 wt.%.
  • This term refers to polymers having an overall positive charge.
  • the cationic polymer has a nitrogen content of from 0.7 to 1.4%.
  • the nitrogen content is from 0.75 to 1.2%, more preferably from 0.8 to 1.1 %.
  • a preferred cationic cellulose polymers is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose)
  • a preferred class of cationic cellulose polymers suitable for this invention are those that have a cellulosic 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.
  • 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 Polyquatemium 10 and is commercially available from The Dow Chemical Company, marketed as the Polymer LR and JR series of polymers. Other polymers are marketed under the SoftCAT tradename from The Dow Chemical Company. 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.
  • 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 Dow Chemical 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 aforementioned cationic cellulose 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 100,000 to 1,000,000 Daltons, even more preferably from 250,000 to 1,000,000 Daltons.
  • the perfume is present in the range from 0.001 to 3 wt.%, preferably from 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • 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 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 from 0.005 to 2 wt.%, 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. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g.
  • Blankophor SN 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 detergent composition may optionally comprise one or more of the following optional ingredients, fatty acids or salts thereof, shading dye, 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.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Thermophos 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 SOKALANTM.
  • SOKALANTM 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 is present in the composition in range from 0.0001 to 0.01 wt %.
  • 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, glycerol, 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.
  • Formulations with a number are according to the invention, formulations with a letter are comparative.
  • PDMS variants of formulations A to D and 1 are not stable (an example is shown as A' in table 2).
  • Towels were assessed by a trained panel of 12 people who assessed the towel for softness vs. the control sample A.
  • Formulation A was given a score of 100.
  • the softening score is an average of the scores from the 12 panellists.
  • Table 3 Formulation Softening Score A 100 B 103 1 176 C 145 D 142
  • Table 3 shows that the best softening score was the combination of the anionic silicone with a cationic cellulose polymer having from 0.7 to 1.4% Nitrogen.
  • the softness was then measured using a Stable Micro Systems Texture Analyser (TA) XT plus with the optional friction module attached.
  • the TA is a commercial instrument incorporating a drive mechanism and a 5 kg load cell.
  • the treated fabric was laid on the horizontal test platform of the instrument and a neoprene rubber cylindrical probe which is attached to the load cell was placed on the fabric surface.
  • the texture analyser is programmed to move the probe over a distance of 40 mm forwards and backwards over the fabric at a speed of 10 mm/s. As the probe moves the software records the frictional force experienced by the probe.
  • Table 4 shows that the lowest friction (and hence most soft fabric) was the one treated with a formulation comprising the combination of the anionic silicone with a cationic cellulose polymer having from 0.7 to 1.4% Nitrogen. This finding agrees with and further confirms the softness data from the panel tests.
  • PDMS variants of formulations E to H and 2 are not stable (an example is shown as E' in table 5).
  • Towels were assessed by a trained panel of 12 people who assessed the towel for softness vs. the control sample A.
  • Formulation A was given a score of 100.
  • the softening score is an average of the scores from the 12 panellists.
  • Table 6 Formulation Softening Score E 100 F 146 2 197 G 156 H 125
  • Table 6 shows that the best softening score was the combination of the anionic silicone with a cationic cellulose polymer having from 0.7 to 1.4% Nitrogen.
  • Table 7 shows that the lowest friction (and hence most soft fabric) was the one treated with a formulation comprising the combination of the anionic silicone with a cationic cellulose polymer having from 0.7 to 1.4% Nitrogen. This finding agrees with and further confirms the softness data from the panel tests.
  • Table 9 shows that the lowest friction scores (and hence most soft fabric) were for those fabrics treated with a formulation comprising the combination of the anionic silicone with a cationic cellulose polymer having from 0.7 to 1.4% Nitrogen.

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 (13)

  1. Composition de détergent de lavage liquide comprenant :
    (a) de 5 à 40 % en masse de tensioactif ;
    (b) de 0,05 à 5 % en masse de silicone anionique adoucissant les textiles ;
    (c) de 0,05 à 2,5 % en masse de polymère de cellulose cationique ayant une teneur en azote de 0,7 à 1,4 % ;
    (d) de 0,001 à 3 % en masse de parfum ; et
    (e) de 0,005 à 2 % en masse de fluorescent.
  2. Composition selon la revendication 1, dans laquelle le silicone anionique présente une masse moléculaire de 1 000 à 100 000, encore mieux de 2 000 à 50 000, bien mieux encore de 5 000 à 50 000, particulièrement de préférence de 10 000 à 50 000.
  3. Composition selon la revendication 1 ou la revendication 2, dans laquelle le silicone anionique présente une teneur en groupe anionique d'au moins 1 % en mol, de préférence 2 % en mol.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle le silicone anionique est présent à une teneur de 0,1 à 2,5 % en masse, de préférence de 0,1 à 2 % en masse.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle le silicone anionique comprend un carboxysilicone.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le silicone est ajouté à la formulation dans la forme d'une émulsion, de préférence dans la forme d'une émulsion non ionique, encore mieux en utilisant un émulsionnant non ionique ramifié.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition de détergent liquide présente un pH de 6 à 10, encore mieux un pH de 6,5 à 9,5, bien mieux encore un pH de 7 à 9, par exemple un pH de 7,5 à 8,5.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère cationique est présent à une teneur de 0,1 à 2 % en masse, de préférence de 0,1 à 1 % en masse, encore mieux de 0,1 à 0,75 % en masse.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle le polymère de cellulose cationique est de l'hydroxyéthylcellulose quaternisé.
  10. Composition selon l'une quelconque des revendications précédentes, dans laquelle le rapport massique du silicone au polymère cationique est de 5:1 à 1:1.
  11. Composition selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif anionique comprend un ou plusieurs du groupe suivant : des benzènesulfonates d'alkyle linéaire, des sulfonates de sodium lauryléther avec en moyenne de 1 à 3 moles d'éthoxylation, des sulfonates d'alkyle primaire, des sulfates de méthyléther et des sulfonates d'alkyle secondaire ou des mélanges de ceux-ci.
  12. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend de plus un ingrédient choisi parmi des acides gras ou sels de ceux-ci, un colorant nuanceur, une enzyme, un polymère anti-redéposition, un polymère inhibant le transfert de colorant, un structurant, un séquestrant, un écran solaire, et/ou un polymère libérant la saleté.
  13. Utilisation d'une composition selon l'une quelconque des revendications 1 à 12 pour assouplir des tissus.
EP14805217.8A 2013-11-27 2014-11-20 Compositions de lavage Active EP3074497B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14805217.8A EP3074497B1 (fr) 2013-11-27 2014-11-20 Compositions de lavage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13194582 2013-11-27
EP14805217.8A EP3074497B1 (fr) 2013-11-27 2014-11-20 Compositions de lavage
PCT/EP2014/075150 WO2015078766A1 (fr) 2013-11-27 2014-11-20 Compositions de blanchisserie

Publications (2)

Publication Number Publication Date
EP3074497A1 EP3074497A1 (fr) 2016-10-05
EP3074497B1 true EP3074497B1 (fr) 2017-05-24

Family

ID=49641670

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14805217.8A Active EP3074497B1 (fr) 2013-11-27 2014-11-20 Compositions de lavage

Country Status (7)

Country Link
EP (1) EP3074497B1 (fr)
CN (1) CN105874049B (fr)
AR (1) AR098531A1 (fr)
BR (1) BR112016011896B1 (fr)
CL (1) CL2016001295A1 (fr)
ES (1) ES2637896T3 (fr)
WO (1) WO2015078766A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11220657B2 (en) 2019-12-31 2022-01-11 Henkel IP & Holding GmbH Solid perfume composition delivering softening
US11447722B2 (en) 2020-01-30 2022-09-20 Henkel Ag & Co. Kgaa Detergent composition for textile softening and anti-redeposition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112019016823B1 (pt) 2017-02-13 2024-01-02 Unilever Ip Holdings B.V. Composição auxiliar para a lavagem de tecidos, método de lavagem de tecidos e uso da composição auxiliar para a lavagem de tecidos
WO2018145898A1 (fr) 2017-02-13 2018-08-16 Unilever Plc Additif pour composition de lessive
CN110291182B (zh) 2017-02-13 2022-04-26 联合利华知识产权控股有限公司 递送洗衣组合物的方法
WO2019166476A1 (fr) * 2018-03-02 2019-09-06 Unilever Plc Compositions de lessive
WO2019166477A1 (fr) * 2018-03-02 2019-09-06 Unilever Plc Compositions de blanchisserie
BR112020017967A2 (pt) 2018-03-02 2020-12-22 Unilever N.V. Método para amaciar malha de algodão e uso do método
EP3874019B1 (fr) 2018-10-29 2022-07-27 Dow Global Technologies LLC Composition d'entretien des tissus comportant de la silicone
US20220220420A1 (en) * 2019-05-16 2022-07-14 Conopco, lnc., d/b/a UNILEVER Laundry composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1567627B1 (fr) * 2002-11-04 2012-08-01 The Procter & Gamble Company Compositions pour traitement de tissus comprenant des polymeres aux charges opposees
JP2006516665A (ja) * 2003-02-03 2006-07-06 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド 洗浄剤配合物及び布地柔軟剤配合物
US20060030513A1 (en) * 2004-08-03 2006-02-09 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Softening laundry detergent
US20060217287A1 (en) * 2005-03-22 2006-09-28 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Fabric softening composition
CN102352284A (zh) * 2011-08-16 2012-02-15 太仓市新鹿染整有限公司 织物柔软调理剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11220657B2 (en) 2019-12-31 2022-01-11 Henkel IP & Holding GmbH Solid perfume composition delivering softening
US11447722B2 (en) 2020-01-30 2022-09-20 Henkel Ag & Co. Kgaa Detergent composition for textile softening and anti-redeposition

Also Published As

Publication number Publication date
WO2015078766A1 (fr) 2015-06-04
AR098531A1 (es) 2016-06-01
CN105874049A (zh) 2016-08-17
CL2016001295A1 (es) 2016-12-09
EP3074497A1 (fr) 2016-10-05
ES2637896T3 (es) 2017-10-17
CN105874049B (zh) 2019-05-03
BR112016011896B1 (pt) 2021-11-23
BR112016011896A2 (pt) 2017-08-08

Similar Documents

Publication Publication Date Title
EP2922936B1 (fr) Compositions de lavage
EP3074497B1 (fr) Compositions de lavage
EP3074496B1 (fr) Compositions pour la lessive
EP2791308B1 (fr) Compositions pour lessiver
EP3074495B1 (fr) Composition de blanchisserie
EP2791310B1 (fr) Compositions de lavage
EP2909295B1 (fr) Compositions détergentes pour le linge
WO2013087285A1 (fr) Compositions pour lessiver et utilisations
EP3212752B1 (fr) Ingrédients de composition de lavage
EP2922938B1 (fr) Compositions de lavage
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: 20160518

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

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

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

Effective date: 20170209

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

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: 896039

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014010161

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170524

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: 896039

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170524

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2637896

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20171017

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: 20170824

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: 20170825

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: 20170524

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: 20170524

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: 20170524

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: 20170524

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: 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: 20170924

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: 20170524

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: 20170524

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: 20170524

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: 20170824

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: 20170524

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: 20170524

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: 20170524

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: 20170524

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: 20170524

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: 20170524

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014010161

Country of ref document: DE

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: 20170524

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: 20170524

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

26N No opposition filed

Effective date: 20180227

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: 20170524

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

Ref country code: CH

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

Effective date: 20171130

Ref country code: LI

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

Effective date: 20171130

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: 20171120

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171130

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: MT

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

Effective date: 20171120

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: 20171120

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: 20171130

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: 20141120

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: 20170524

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

Ref country code: CY

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

Effective date: 20170524

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: 20170524

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

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: 20170524

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: 20170524

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602014010161

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: GB

Payment date: 20231123

Year of fee payment: 10

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

Ref country code: TR

Payment date: 20231117

Year of fee payment: 10

Ref country code: IT

Payment date: 20231121

Year of fee payment: 10

Ref country code: FR

Payment date: 20231120

Year of fee payment: 10

Ref country code: DE

Payment date: 20231121

Year of fee payment: 10

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

Ref country code: ES

Payment date: 20240129

Year of fee payment: 10