EP3303535B1 - Composition de détergent pour lessive - Google Patents

Composition de détergent pour lessive Download PDF

Info

Publication number
EP3303535B1
EP3303535B1 EP16718680.8A EP16718680A EP3303535B1 EP 3303535 B1 EP3303535 B1 EP 3303535B1 EP 16718680 A EP16718680 A EP 16718680A EP 3303535 B1 EP3303535 B1 EP 3303535B1
Authority
EP
European Patent Office
Prior art keywords
laundry detergent
detergent composition
alkyl
composition according
alkyl ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16718680.8A
Other languages
German (de)
English (en)
Other versions
EP3303535A1 (fr
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Dietmar Andreas LANG
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
Publication of EP3303535A1 publication Critical patent/EP3303535A1/fr
Application granted granted Critical
Publication of EP3303535B1 publication Critical patent/EP3303535B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present Invention provides and enzymatic and dispersant formulation for use in domestic laundry.
  • Laundry detergent formulations containing a high fraction of anionic surfactant relative to non-ionic surfactant are ubiquitous.
  • Metalloprotease enzymes are used in laundry detergent formulations to remove protein containing stains from fabrics.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • US 5 269 960 discloses stable liquid, aqueous enzyme detergent comprising a mixture of nonionic and anionic surfactants, enzymes and a calcium ion source as an enzyme stabilizer, and an alkyl ether carboxylate as a phase stabilizer.
  • DE33320340 discloses a liquid phosphate-free detergent composition containing an enzyme, e.g. protease, which is stabilised with an alkoxylated carboxylic acid salt.
  • the present invention provides a laundry detergent composition comprising:
  • the wt% of anionic surfactants are calculated as the sodium salt.
  • the wt% of the alkyl ether carboxylic acid dispersant is calculated as the COOH form.
  • the present invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • Preferably powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of 9.5-11.
  • the laundry detergent is an aqueous liquid laundry detergent, preferably with a pH of from 7 to 9.
  • Metalloproteases is a class of hydrolases which cleave peptide bonds by the action of a water molecule which is activated by complexing to at least one bivalent metal ions belonging to the group of zinc, manganese, cobalt, nickel or copper ions, preferably zinc.
  • the protease is an M4 metalloprotease, most preferably a neutral metalloprotease.
  • the metallo-proteases that may be used in this invention includes any of those which may be used in a homecare application.
  • These metallo-proteases are, for example, derived from bacterium selected from the group consisting bacillus amyloliquefaciens, bacillus subtilis, bacillus stearothermophilus, and bacillus thermoproteolyticus, and fungi selected from the group consisting Aspergillus oryzae and Aspergillus niger.
  • M4 Metalloprotease Family or "M4 Metalloprotease” or “M4" as used herein means a polypeptide falling into the M4 metalloprotease family according to Rawlings et al., Biochem. J., 290, 205-218 (1993 ) and as further described in MEROPS - ( Rawlings et al. , MEROPS: the peptidase database, Nucl Acids Res, 34 Database issue, D270-272, 2006 ).
  • the M4 metalloproteases are neutral metalloproteases containing mainly endopeptidases. All peptidases in the family bind a single, catalytic zinc ion.
  • M4 metalloprotease family members include the common HEXXH motif, where the histidine residues serve as zinc ligands and glutamate is an active site residue. M4 metalloproteases have a pH optimum mainly at neutral pH.
  • the M4 metalloprotease family includes, e.g., NeutraseTM (Novozymes) (classified as MEROPS subclass M04.014), Thermolysin, Bacillolysin, vibriolysin, pseudolysin, Msp peptidase, coccolysin, aureolysin, vimelysin, lambda toxin neutral peptidase B, PA peptidase (Aeromonas- type), griselysin, stearolysin, Mprlll (Alteromonas sp.
  • strain 0-7 pap6 peptidase, neutral peptidase (Thermoactinomyces-type), ZmpA peptidase (Burkholderia sp.), zpx peptidase, PrtS peptidase (Photorhabdus luminescens), protealysin, ZmpB peptidase (Burkholderia sp.).
  • the M4 metalloprotease family of polypeptides have been further characterized and presently includes, according to MEROPS, at least twenty-two subclasses for which a distinct MEROPS ID (i.e., an identifier of the formula M04.xxx) has been assigned, as well as non-peptidase homologues and unassigned peptidases.
  • MEROPS a distinct MEROPS ID (i.e., an identifier of the formula M04.xxx) has been assigned, as well as non-peptidase homologues and unassigned peptidases.
  • Thermolysin-Like Metalloprotease as used herein means (a) an M4 metalloprotease of the MEROPS subclass M04.001 ; (b) an M4 metalloprotease of the MEROPS subclass M04.018; (c) an M4 metalloprotease of the MEROPS subclass M04.021; (d) an M4 metal loprotease having an active cleft motif: TG[TS] [QS] D N GGVH [Tl] ; (e) an M4 metalloprotease having an active cleft motif: DPDHSKRYTG[TS][QS]DNGGVH[TI]NSGI; and (f) an M4 metalloprotease having an active cleft motif: NT[TS][QS]DNGGVH[TI]NSGI.
  • the TLPs consist of an alpha-helical C-terminal domain and an N-terminal domain mainly consisting of beta-strands.
  • the domains are connected by a central alpha-helix. This helix is located at the bottom of the active site cleft and contains several of the catalytically important residues such as four substrate binding pockets S2, Si, Si' and S2' have been identified ( Hangauer et al. (1984) Biochemistry 23:5730-5741 )
  • alkyl ether carboxylic acid dispersants are not included as anionic surfactants. Weights of alkyl ether carboxylic acid are calculated as the protonated form, R-(OCH 2 CH 2 ) n -OCH 2 COOH. They may be used as salt version for example sodium salt, or amine salt.
  • the alkyl chain may be linear or branched, preferably it is linear.
  • the alkyl chain may be aliphatic or contain one cis-double bond.
  • Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®)
  • the laundry composition comprises anionic charged surfactant (which includes a mixture of the same).
  • Suitable anionic detergent compounds which may be used are usually 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 alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulphonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
  • the most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof.
  • the alkyl ether sulphate is a C 12 -C 14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyl benzene sulphonate is a sodium C 11 to C 15 alkyl benzene sulphonates.
  • the alkyl sulphates is a linear or branched sodium C 12 to C 18 alkyl sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
  • the level of anionic surfactant in the laundry composition is preferably from (i) 5 to 50 wt% negatively charged surfactant, preferably the level of negatively charged surfactant is from 6 to 30 wt%, more preferably 8 to 20 wt%.
  • two or more anionic surfactant are present, preferably linear alkyl benzene sulphonate together with an alkyl ether sulphate.
  • Non-ionic surfactant may be present in the surfactant mix.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • Preferred nonionic detergent compounds are the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide.
  • the alkyl ethoxylated non-ionic surfactant is a C 8 to C 18 primary alcohol with an average ethoxylation of 7EO to 9EO units.
  • Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
  • zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
  • composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • Zeolite and carbonate are preferred builders for powder detergents.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 O. Al 2 O 3 . 0.8-6 SiO2 where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • the ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
  • phosphate builders may be used.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • the powder laundry detergent formulation is carbonate built.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, 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-sulfostyryl)biphenyl.
  • the aqueous solution used in the method has a fluorescer present.
  • a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • 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.
  • Perfume and top note may be used to cue the whiteness benefit of the invention.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more further polymers.
  • suitable polymers are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the formulation.
  • One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is preferably selected from: amylases lipases; and, cellulases.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as 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 such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • a polyol such as 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 such as 4-formylphenyl boronic acid
  • Shading dyes are preferably present in the formulation at a level from 0.002 to 0.2 wt%.
  • Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003 ) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003 ).
  • Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol -1 cm -1 , preferably greater than 10000 L mol -1 cm -1 .
  • the dyes are blue or violet in colour.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
  • Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged.
  • Azine preferably carry a net anionic or cationic charge.
  • Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280.
  • the white cloth used in this test is bleached non-mercerised woven cotton sheeting.
  • Shading dyes are discussed in WO2005/003274 , WO2006/032327 (Unilever), WO 2006/032397 (Unilever), WO2006/045275 (Unilever), WO06/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO2009/132870 (Unilever), WO 2009/141173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO2011/011799 (P&G), WO2012/054820 (P&G), WO2013/142495 (P&G), and WO2013/151970 (P&G).
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497 . Preferred examples of thiophene dyes are shown below: and,
  • Bis-azo dyes are preferably sulphonated bis-azo dyes.
  • Preferred examples of sulphonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, Direct Violet 66, direct violet 99 and alkoxylated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906 .
  • alkoxylated bis-azo dye is :
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from: wherein:
  • the shading dye is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • Preferred reactive anthraquinone dyes are: Reactive blue 1; Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101; Reactive blue103; Reactive blue114; Reactive blue117; Reactive blue125; Reactive blue141; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164; Reactive blue 166; Reactive blue 177; Reactive blue 181; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive
  • the dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.
  • the formulation was used to wash eight 5x5cm EMPA 117 stain monitor (blood/milk/ink stain on polycotton) in a tergotometer set at 200rpm. A 20 minute wash was conducted in 800ml of 26° French Hard water at 35°C, with 2.3g/L of the formulation. To simulate oily soil (12.5g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
  • metalloprotease and alkyl ether carboxylic acid increases the stain removal as seen by higher L* values.
  • the combination of metalloprotease with the alkyl ether carboxylic acid gives a greater increase in L* than expected from the effect of the protease and alkyl ether carboxylic acid alone where a value of 57.78 is expected and 61.31 obtained.

Claims (11)

  1. Composition de détergent de lessive comprenant :
    (i) de 5 à 50 % en masse d'un tensioactif, différent d'un dispersant d'acide alkyléthercarboxylique choisi parmi : des tensioactifs anioniques et non-ioniques ;
    dans laquelle la fraction massique de tensioactif non-ionique/tensioactif anionique est de 0 à 0,3 ;
    (ii) de 0,5 à 20 % en masse d'un dispersant d'acide alkyléthercarboxylique de la structure suivante :

            R-(OCH2CH2)n-OCH2-COOH,

    dans laquelle :
    R est choisi parmi des chaînes alkyle linéaires ou ramifiées en C10 à C26 saturées et mono-insaturées, et dans laquelle n est choisi de 5 à 20 ; et,
    (iii) de 0,0005 à 0,2 % en masse d'une enzyme de métalloprotéase M4,
    dans laquelle la formulation de détergent de lessive contient moins de 1 % en masse de phosphate.
  2. Composition de détergent de lessive selon la revendication 1, dans laquelle le tensioactif anionique est choisi parmi : des benzènesulfonates d'alkyle linéaires ; sulfates d'alkyle ; sulfates d'alkyléthers ; et mélanges de ceux-ci, et le tensioactif non-ionique est choisi parmi : des alkyléthers avec de 7 à 9 groupes éthoxy.
  3. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle R est choisi parmi des chaînes alkyle linéaires ou ramifiées en C12 à C24, de préférence une chaîne alkyle linéaire en C16 à C20.
  4. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle n est choisi de 7 à 13, de préférence de 8 à 12.
  5. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle la composition est un détergent liquide de lessive aqueux.
  6. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle n est choisi entre 9,5 et 10,5.
  7. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle le dispersant d'acide alkyléthercarboxylique est :

            CH3(CH2)7CH=CH(CH2)8(OCH2CH2)10OCH2COOH.

  8. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle les tensioactifs anioniques et non-ioniques est/sont présent(s) dans l'intervalle de 8 à 20 % en masse.
  9. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle la fraction massique de tensioactif non-ionique/tensioactif anionique est de 0,05 à 0,12.
  10. Composition de détergent de lessive selon l'une quelconque des revendications précédentes, dans laquelle le dispersant d'acide alkyléthercarboxylique est présent dans l'intervalle de 1,5 à 10 % en masse.
  11. Procédé domestique de traitement d'un textile, le procédé comprenant les étapes de :
    (i) traitement d'un textile avec 1 g/L d'une solution aqueuse de la composition de détergent de lessive selon l'une quelconque des revendications précédentes ; et,
    (ii) le laisser ladite solution de détergent de lessive aqueuse rester en contact avec le textile pendant de 10 minutes à 2 jours puis le rinçage et séchage du textile.
EP16718680.8A 2015-05-27 2016-04-26 Composition de détergent pour lessive Active EP3303535B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15169368 2015-05-27
PCT/EP2016/059296 WO2016188693A1 (fr) 2015-05-27 2016-04-26 Composition détergente à lessive

Publications (2)

Publication Number Publication Date
EP3303535A1 EP3303535A1 (fr) 2018-04-11
EP3303535B1 true EP3303535B1 (fr) 2018-10-03

Family

ID=53199896

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16718680.8A Active EP3303535B1 (fr) 2015-05-27 2016-04-26 Composition de détergent pour lessive

Country Status (5)

Country Link
EP (1) EP3303535B1 (fr)
CN (1) CN109072130B (fr)
BR (1) BR112017024403B1 (fr)
WO (1) WO2016188693A1 (fr)
ZA (1) ZA201707150B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112019011999B1 (pt) * 2016-12-15 2022-11-08 Unilever Ip Holdings B.V Composição de detergente líquida aquosa para lavagem de roupas e método doméstico de tratamento de um tecido

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8202294A (nl) * 1982-06-07 1984-01-02 Chem Y Vloeibaar fosfaatvrij wasmiddel.
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
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
JP3219765B2 (ja) 1991-04-30 2001-10-15 ザ、プロクター、エンド、ギャンブル、カンパニー タンパク分解酵素を阻害するためのホウ酸系物質−ポリオール複合体を有するビルダー入り液体洗剤
WO2002036727A1 (fr) * 2000-01-14 2002-05-10 The Procter & Gamble Company Composition detergente contenant une metalloprotease et ion calcium
GB0314210D0 (en) 2003-06-18 2003-07-23 Unilever Plc Laundry treatment compositions
GB0420203D0 (en) 2004-09-11 2004-10-13 Unilever Plc Laundry treatment compositions
CN101023158B (zh) 2004-09-23 2011-04-27 荷兰联合利华有限公司 洗衣处理组合物
GB0421145D0 (en) 2004-09-23 2004-10-27 Unilever Plc Laundry treatment compositions
DE102004052007B4 (de) 2004-10-25 2007-12-06 Müller Weingarten AG Antriebssystem einer Umformpresse
ATE443753T1 (de) 2006-08-10 2009-10-15 Unilever Nv Nuancierungsmittel
PL2192169T3 (pl) 2007-01-19 2012-10-31 Procter & Gamble Kompozycja środka piorącego zawierająca środki wybielające dla substratów celulozowych
ES2387142T3 (es) 2007-05-18 2012-09-14 Unilever N.V. Colorantes de trifenodioxazina
BRPI0910682B1 (pt) 2008-05-02 2020-09-24 Unilever N.V. Grânulo de corante tonalizante que produzem menos manchas, e, composição detergente granular para lavar roupas
BRPI0912868B1 (pt) 2008-05-20 2020-10-27 Unilever N.V. composição de tratamento para lavagem e método caseiro para tratamento de têxteis
MY159509A (en) 2009-03-05 2017-01-13 Unilever Plc Dye radical initiators
MY154041A (en) 2009-03-12 2015-04-30 Unilever Plc Dye-polymers formulations
WO2010148624A1 (fr) 2009-06-26 2010-12-29 Unilever Plc Polymères colorants
CN103270118B (zh) 2010-10-22 2015-05-13 美利肯公司 用作上蓝剂的二偶氮着色剂
WO2012054058A1 (fr) 2010-10-22 2012-04-26 The Procter & Gamble Company Colorants bis-azoïques destinés à être utilisés à titre d'agents de bleuissement
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
EP2638142B1 (fr) 2010-11-12 2017-05-10 The Procter and Gamble Company Colorants azoïques thiophéniques et compositions de lessive les contenant
MX2013009176A (es) * 2011-02-16 2013-08-29 Novozymes As Composiciones detergentes que comprenden metaloproteasas.
CN103476915A (zh) * 2011-02-16 2013-12-25 诺维信公司 包含金属蛋白酶的去污剂组合物
EP2675882A1 (fr) * 2011-02-16 2013-12-25 Novozymes A/S Composition de détergent comprenant des métalloprotéases m7 ou m35
EP2791310B1 (fr) * 2011-12-12 2017-01-18 Unilever Plc. Compositions de lavage
WO2013142486A1 (fr) 2012-03-19 2013-09-26 The Procter & Gamble Company Compositions d'entretien du linge contenant des colorants
EP2834340B1 (fr) 2012-04-03 2016-06-29 The Procter and Gamble Company Composition détergente pour la lessive comprenant un composé de phtalocyanine soluble dans l'eau

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
WO2016188693A1 (fr) 2016-12-01
BR112017024403B1 (pt) 2022-03-08
ZA201707150B (en) 2019-02-27
CN109072130A (zh) 2018-12-21
CN109072130B (zh) 2020-10-27
BR112017024403A2 (pt) 2018-07-24
EP3303535A1 (fr) 2018-04-11

Similar Documents

Publication Publication Date Title
EP3356505B1 (fr) Composition détergente à lessive
CN107592883B (zh) 洗衣洗涤剂组合物
EP3356503B1 (fr) Composition detergente liquide à lessive
AU2017267050B2 (en) Liquid laundry detergent compositions
EP3303535B1 (fr) Composition de détergent pour lessive
EP3529342B1 (fr) Composition d'agent azurant
EP3519542B1 (fr) Procédé de lavage du linge domestique
EP3303537B1 (fr) Composition de détergent pour lessive
AU2017267127B2 (en) Liquid laundry detergent compositions
EP3417040B1 (fr) Composition de blanchiment
EP3256557B1 (fr) Composition de lessive liquide
EP3303536B1 (fr) Composition de détergent pour lessive
EP3417039B1 (fr) Composition de blanchiment
EP3256558B1 (fr) Composition liquide de lessive

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20171113

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

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

Effective date: 20180620

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: AT

Ref legal event code: REF

Ref document number: 1048615

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181015

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016006251

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20181003

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: 1048615

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181003

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

Ref country code: NL

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

Effective date: 20181003

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: 20181003

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: 20181003

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: 20181003

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: 20181003

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: 20181003

Ref country code: ES

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: 20181003

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: 20181003

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: 20181003

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: 20190103

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: 20190103

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: 20190203

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

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: 20190104

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: 20181003

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: 20181003

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: 20190203

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: 20181003

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016006251

Country of ref document: DE

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

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: 20181003

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: 20181003

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: 20181003

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: 20181003

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: 20181003

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: 20181003

26N No opposition filed

Effective date: 20190704

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190430

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: 20181003

Ref country code: LU

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

Effective date: 20190426

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: 20190430

Ref country code: LI

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

Effective date: 20190430

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: 20190430

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: 20190426

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: 20181003

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: 20160426

Ref country code: MT

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

Effective date: 20181003

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602016006251

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER NV, ROTTERDAM, NL

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: 20181003

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

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: 20181003

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

Ref country code: FR

Payment date: 20230424

Year of fee payment: 8

Ref country code: DE

Payment date: 20220620

Year of fee payment: 8

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

Ref country code: TR

Payment date: 20230424

Year of fee payment: 8

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

Ref country code: GB

Payment date: 20230419

Year of fee payment: 8