EP3519542A1 - Domestic laundering method - Google Patents

Domestic laundering method

Info

Publication number
EP3519542A1
EP3519542A1 EP17776999.9A EP17776999A EP3519542A1 EP 3519542 A1 EP3519542 A1 EP 3519542A1 EP 17776999 A EP17776999 A EP 17776999A EP 3519542 A1 EP3519542 A1 EP 3519542A1
Authority
EP
European Patent Office
Prior art keywords
wash
iii
wash method
rinse conditioner
anionic surfactant
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.)
Granted
Application number
EP17776999.9A
Other languages
German (de)
French (fr)
Other versions
EP3519542B1 (en
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
David Stephen Grainger
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 Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=57018034&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3519542(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP3519542A1 publication Critical patent/EP3519542A1/en
Application granted granted Critical
Publication of EP3519542B1 publication Critical patent/EP3519542B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention provides a method for cleaning clothes in domestic laundry.
  • Rinse formulations containing quaternary ammonium compounds having at least one C12 to C22 alkyl chain for softening clothes are ubiquitous.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • EP0154380 discloses a laundering agent which contains active detergent, builders, a combination of polyphosphate with zeolite as sequestering agent and, if desired, further usual additives, wherein the sequestering effect of the polyphosphate-zeolite combination is enhanced by an ethercarboxylic acid of the formula RO-(C2H40)x-CH2COOM or R-CO-NH- (C2H40)x-CH2COOM, wherein R is the residue of an aliphatic or alkyl aromatic
  • US374191 1 discloses a detergent composition, preferably phosphate-free, built using conventional builders, optionally including an organic sequestering agent, and contains as the active 15 system a coacervate system containing an alkyl or alkyl-aryl polyoxyalkylene carboxylic acid and a non-ionic detergent.
  • the coacervate system is suitable for washing fabrics and for use in automatic dish washing machines.
  • the present invention provides a wash method, the wash method comprising the sequential steps of:
  • the rinse conditioner comprises from 1 to 25 wt%, preferably 3 to 15 wt%, of a quaternary ammonium compound wherein in step (i) the quaternary ammonium compound has the general formula (I):
  • Ri , R2, R3 and R 4 are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R 4 are selected from C10 to C20 hydrocarbons group;
  • X is an anion
  • y is the valence of X
  • R-(OCH 2 CH2)n-OCH2-COOH wherein R is a saturated or mono-unsaturated C10 to C18 alkyl chain, preferably R is selected from the group consisting of: lauryl; stearyl; and;, oleyl alkyl chain, and n is greater than 4, more preferably from 5 to 20, most preferably from 10 to 20; and,
  • the treatment steps (i) and (iii) preferably take from 5 to 120 minutes each.
  • the wt% of anionic surfactants are calculated as the sodium salt.
  • 'a' or 'an' is used in reference to a class of ingredients, this can refer equally to one or one or more of the ingredient (i.e. to a single ingredient, or to a mixture of two or more of the ingredients).
  • an anionic surfactant can mean a single anionic surfactant or a mixture of anionic surfactants.
  • step (i) the quaternary ammonium compound has the general formula (I):
  • Ri , R2, R3 and R 4 are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R 4 are selected from C10 to C20 hydrocarbons group;
  • X is an anion
  • the quaternary ammonium compound preferably has the general formula (I):
  • R2, 3 and R 4 are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R 4 , preferably at least 2 of Ri , R2, R3 and R 4 , are selected from C10 to C20 hydrocarbons group, preferably C12 to C18.
  • the hydrocarbon groups are linear alkyl chains that are saturated or mono-unsaturated.
  • X is an anion; or example halide, such as CI or Br, sulphate, alkyl sulphate, nitrate or acetate; y is the valence of X.
  • quaternary ammonium compounds are:
  • TET Di(tallowcarboxyethyl)hydroxyethyl methyl ammonium methylsulfate
  • TEO Di(oleocarboxyethyl)hydroxyethyl methyl ammonium methylsulfate
  • TES Distearyl hydroxyethyl methyl ammonium methylsulfate
  • TEHT Di(hydrogenated tallow-carboxyethyl)hydroxyethyl methyl ammonium methylsulfate
  • TEP Di(palmiticcarboxyethyl)hydroxyethyl methyl ammonium methylsulfate
  • DEEDMAC Dimethylbis[2-[(1-oxooctadecyl)oxy]ethyl]ammonium chloride
  • DHT Dihydrogenated tallowdimethylammonium chloride.
  • TEAQ methyl bis-[ethyl (tallowoyl)]- 2-hydroxyethyl ammonium methyl sulphate.
  • the rinse conditioner has a pH of less than 7. More preferably the rinse conditioner has a pH of from 3 to 6.5.
  • the pH of the aqueous solution of step (i) is less than 7, more preferably from pH 3 to 6.5.
  • This in use pH is provided by the rinse conditioner formulation.
  • the in use pH can be measured for example by measuring an aqueous solution of the rinse conditioner dosed at 1 g/L.
  • the rinse conditioner used in step (i) comprises at most 1 % anionic surfactant. More preferably the rinse conditioner is free from anionic surfactant. Preferably the rinse conditioner used in step (i) comprises at most 1 % nonionic surfactant. More preferably the rinse conditioner is free from nonionic surfactant.
  • the main wash detergent formulation may be a powder, liquid or gel.
  • the main wash detergent formulation is preferably a non-phosphate laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • the pH of the aqueous solution of step (iii) is from pH 7 to 1 1 .
  • This in use pH is provided by the main wash detergent formulation.
  • the in use pH can be measured for example by measuring an aqueous solution of the main wash detergent dosed at 1 g/L.
  • Powder laundry detergent formulations are predominantly carbonate built, i.e. the weight% of sodium carbonate is greater than the weight % sum of other builder ingredient present, preferably the weight% level of other builder materials is less than 30%, more preferably less than 15 wt% of the weight% level of sodium carbonate. Powders, should preferably give an in use pH of from 9.5 to 1 1 .
  • Liquid detergent formulations should preferably give an in use pH of from 7 to 9.
  • the main wash detergent formulation are powder laundry detergent formulations.
  • the main wash detergent formulations used in step (iii) comprises at most 1 % quaternary ammonium compounds. More preferably the main wash detergent is free from quaternary ammonium compounds.
  • the main wash detergent formulation may be present in a polvyinylalcohol pouch for ease of dispensing.
  • the main wash detergent formulation may contain non-ionic surfactant preferably wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0 to 0.12;
  • the main wash detergent formulation contains from 0.002 to 0.2wt% of a subtilisin protease enzyme, preferably from 0.005 to 0.05 wt%;
  • Alkyl Ether Carboxylic acid have the form: R-(OCH2CH2) n -OCH2-COOH, wherein R is saturated or mono-unsaturated alkyl chain and n is preferably greater than 4, preferably selected from 5 to 20, most preferably 10 to 20, even more preferably from 15 to 20.
  • Alkyl Ether Carboxylic acid may be used as salt version for example sodium salt, or amine salt. So for the avoidance of doubt, where the acid form of the alkyl ether carboxylic acid is stated, or depicted, it is also intended to include carboxylate salts of the acid form.
  • the alkyl chain is preferably selected from: oleyl, Palmitoleyl, CH3(CH2)9-; CH3(CH2)i CH 3 (CH 2 )ii-; CH 3 (CH 2 )i2-; CH 3 (CH 2 )i 3 -; CH 3 (CH 2 )i 4 -; CH 3 (CH 2 )i 5 -; CH 3 (CH 2 )i 6 -; and,
  • CH 3 (CH 2 )i7- More preferably CH 3 (CH 2 )n-; CH 3 (CH 2 )i 7 - and oleyl ; most preferably
  • Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
  • Alkyl ether carboxylic acids may be prepared by the modified Williamson synthesis:
  • the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder.
  • the main wash detergent formulation comprises anionic charged surfactant (which includes a mixture of the same).
  • Alkyl ether carboxylate are included as anionic charged surfactant.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal or amine salts of fatty acids (soaps), organic sulphates and sulphonates having alkyi radicals containing from about 8 to about 22 carbon atoms, the term alkyi being used to include the alkyi portion of higher alkyi radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyi sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyi Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyi C10 to C15 benzene sulphonates; and sodium alkyi 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 alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; soaps; alkyi (preferably methyl) ester sulphonates, and mixtures thereof.
  • the most preferred anionic surfactants are selected from: linear alkyi benzene sulphonates; alkyi sulphates; soaps; alkyi ether sulphates and mixtures thereof.
  • the alkyi ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyi benzene sulphonate is a sodium Cn to C15 alkyi benzene sulphonates (LAS).
  • the alkyi sulphates is a linear or branched sodium C12 to Cie alkyi sulphates.
  • SDS sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyi sulphate). Soaps are preferably C12 to C18 saturated fatty acids, preferably they are present at levels of less than 3wt% of the formulation.
  • LAS is the dominant anionic surfactant present. It is preferably that >80wt% of the anionic surfactant present is LAS.
  • liquid detergents it is preferably that >70wt% of the anionic surfactant are selected from LAS and SLES.
  • 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 Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide.
  • the non-ionic surfactant is an alkyl ethoxylated non-ionic surfactant and is a Cs to Cie primary alcohol, most preferably a C12-C16 primary alcohol, with an average ethoxylation of 7EO to 9EO units.
  • Subtilisin protease enzymes (EC 3.4.21 .62) hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • Subtilisin protease enzymes are members of the subtilase type serine proteases family.
  • subtilases refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523.
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 sub-divisions, of which the Subtilisin family is one.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B.
  • subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, * 36D, V68A, N76D, N87S,R, * 97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H 120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • protease provides enhances cleaning in combination with the method.
  • the protease enzyme is preferably granulated and post-dosed into the powder.
  • the enzyme granules have a particle size smaller than 2 mm, as determined using graded sieves.
  • the enzyme granules have a particle size from 0.2 to 1.5mm as determined using graded sieves.
  • Subtilisin are commercially available, for example, from NovozymesTM and GenencorTM
  • the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder. Builders or Complexinq Agents
  • the main wash formulation preferably contains a builder or complexing agent.
  • Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials 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.
  • the main wash formulation 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.
  • 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 main wash formulation 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 5%wt.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 0. AI2O3. 0.8-6 Si02 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
  • the preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • aluminosilicate builders include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) may be present.
  • silicates such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) may be present.
  • Spray drying of the powder detergent is preferred.
  • the main wash formulation 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 main wash 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 rinse conditioner and main wash formulation both 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
  • perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. It is commonplace for a plurality of perfume components to be present in a formulation. In the 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. Encapsulated perfume may be used. In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by
  • 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 cleaning and whiteness benefit of the invention.
  • the main wash formulation may comprise one or more further polymers.
  • examples are carboxymethylcellulose, ethoxylated polyethyleneimine (EPEI), polymeric ester of aromatic dicarboxylic acids, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • EPEI is preferably a base (unreacted) polyethylene imine of 400 to 1200 molecular weight that has been ethoxylated with 10 to 30 mole equivalent of ethylene oxide per N-H in the a base (unreacted) polyethylene imine.
  • One or more further enzymes are preferred present in main wash formulation and when practicing a method of the invention.
  • the level of each further enzyme in the main wash formulation of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is preferably selected from: amylases, Mannanases, lipases; and, cellulases, most preferably amylases and lipases.
  • Suitable lipases include those sold under the tradenames lipex®, Lipoclean® and Lipolex® by Novozymes, Bagsvaerd Denmark.
  • Any enzyme present in the main wash formulation 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 main wash formulation 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.
  • 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.
  • WO 2006/032397 (Unilever), WO2006/045275 (Unilever), WO06/027086 (Unilever), WO 2008/017570 (Unilever), WO 2008/141880 (Unilever), WO2009/132870 (Unilever), WO 2009/141 173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO201 1/01 1799 (P&G),
  • Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes.
  • 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 1 1 , 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..
  • An example of an 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:
  • X 3 is selected from: -H; -F; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and, -OC 2 H 5 ;
  • X 4 is selected from: -H; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and, -OC 2 H 5 ;
  • Y 2 is selected from: -OH; -OCH 2 CH 2 OH; -CH(OH)CH 2 OH; -OC(0)CH 3 ; and, C(0)OCH 3 .
  • the shading dye is present is present in the composition in range from 0.0001 to
  • the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.
  • the carbonate built powder detergent formulations are present in 0.5 to 5kg packs.
  • Sokalan CP5 (BASF) 0.4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A laundry washing method comprising the sequential steps of: (i) agitating a textile garment in an aqueous solution of 0.5-10g/L of a rinse conditioner comprising 1-25 wt% of a quaternary ammonium compound having the general formula (I): [N+(R1)(R2)(R3)(R4)]y X- (I), wherein: • R1-R 4, are independently selected from a C1-C30 hydrocarbon group; wherein at least one of R 1-R 4 are selected from C10-C20 hydrocarbons group; • X is an anion; • y is the valence of X; (ii) drying the textile garment; (iii) agitating the textile garment in an aqueous solution of 0.5-10g/L of a main wash detergent formulation comprising 5-40 wt% of anionic surfactant, the anionic surfactant providing 0.02-1 g/L, of an alkyl ether carboxylic acid or carboxylate salt thereof of the following structure: R-(OCH2CH2)n-OCH2-COOH, wherein R is a saturated or mono-unsaturated C10-C18 alkyl chain and n>4.

Description

DOMESTIC LAUNDERING METHOD
Field of Invention
The present invention provides a method for cleaning clothes in domestic laundry. Background of Invention
Main wash detergent formulations containing anionic surfactant for cleaning clothes surfactant are ubiquitous.
Rinse formulations containing quaternary ammonium compounds having at least one C12 to C22 alkyl chain for softening clothes are ubiquitous.
WO2013/087286 (Unilever) discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
US5269960 (Clorox) discloses liquid aqueous enzyme detergent containing enzymes, non- ionic surfactant, fatty acid and alkyl ether carboxylic acids that have enhanced physical and enzyme stability.
EP0154380 discloses a laundering agent which contains active detergent, builders, a combination of polyphosphate with zeolite as sequestering agent and, if desired, further usual additives, wherein the sequestering effect of the polyphosphate-zeolite combination is enhanced by an ethercarboxylic acid of the formula RO-(C2H40)x-CH2COOM or R-CO-NH- (C2H40)x-CH2COOM, wherein R is the residue of an aliphatic or alkyl aromatic
hydrocarbon having at least 8 carbon atoms, x is a number having an average value of 0.5-20 and M is hydrogen or a cation permissible in laundering agents, said polyether carboxylic acid being present in an amount of 0.3 to 10 percent, preferably 0.3 to 5 percent, based on the entire composition.
US374191 1 discloses a detergent composition, preferably phosphate-free, built using conventional builders, optionally including an organic sequestering agent, and contains as the active 15 system a coacervate system containing an alkyl or alkyl-aryl polyoxyalkylene carboxylic acid and a non-ionic detergent. The coacervate system is suitable for washing fabrics and for use in automatic dish washing machines. Summary of the Invention
There is a need to increase cleaning in wash methods that combine main wash detergent formulations containing anionic surfactant and rinse conditioners containing quaternary ammonium compound.
We have found that the use of a rinse conditioner containing quaternary ammonium compounds in combination with a main wash detergent containing an alkyl ether carboxylate provides enhanced cleaning benefits.
In one aspect the present invention provides a wash method, the wash method comprising the sequential steps of:
(i) agitating a textile garment in an aqueous solution of from 0.5 to 10g/L of a rinse
conditioner, wherein the rinse conditioner comprises from 1 to 25 wt%, preferably 3 to 15 wt%, of a quaternary ammonium compound wherein in step (i) the quaternary ammonium compound has the general formula (I):
[N+(R1)(R2)(R3)(R4)]y X- (I), wherein:
Ri , R2, R3 and R4, are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R4 are selected from C10 to C20 hydrocarbons group;
X is an anion; and,
y is the valence of X;
(ii) drying the textile garment;
(iii) agitating the textile garment in an aqueous solution of from 0.5 to 10g/L of a main wash detergent formulation comprising from 5 to 40 wt%, preferably 10 to 20 wt%, of an anionic surfactant, the anionic surfactant providing from 0.02 to 1 g/L, preferably 0.04 to 0.4g/L, of an alkyl ether carboxylic acid or carboxylate salt thereof of the following structure:
R-(OCH2CH2)n-OCH2-COOH, wherein R is a saturated or mono-unsaturated C10 to C18 alkyl chain, preferably R is selected from the group consisting of: lauryl; stearyl; and;, oleyl alkyl chain, and n is greater than 4, more preferably from 5 to 20, most preferably from 10 to 20; and,
(iv) optionally treating again with the rinse conditioner and drying the fabric.
The treatment steps (i) and (iii) preferably take from 5 to 120 minutes each. The wt% of anionic surfactants are calculated as the sodium salt. Detailed Description of the Invention
Where 'a' or 'an' is used in reference to a class of ingredients, this can refer equally to one or one or more of the ingredient (i.e. to a single ingredient, or to a mixture of two or more of the ingredients). For example 5 to 40 wt.% of an anionic surfactant can mean a single anionic surfactant or a mixture of anionic surfactants.
Rinse conditioner
In step (i) the quaternary ammonium compound has the general formula (I):
[N+(R1)(R2)(R3)(R4)]y X- (I),
wherein:
Ri , R2, R3 and R4, are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R4 are selected from C10 to C20 hydrocarbons group;
X is an anion; and,
y is the valence of X
The quaternary ammonium compound preferably has the general formula (I):
[N+(Ri)(R2)(R3)(R4)]y X- (I) wherein:
i , R2, 3 and R4, are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least 1 one of Ri , R2, R3 and R4, preferably at least 2 of Ri , R2, R3 and R4, are selected from C10 to C20 hydrocarbons group, preferably C12 to C18. Preferably the hydrocarbon groups are linear alkyl chains that are saturated or mono-unsaturated.
X is an anion; or example halide, such as CI or Br, sulphate, alkyl sulphate, nitrate or acetate; y is the valence of X.
Preferred examples of quaternary ammonium compounds are:
TET : Di(tallowcarboxyethyl)hydroxyethyl methyl ammonium methylsulfate;
TEO : Di(oleocarboxyethyl)hydroxyethyl methyl ammonium methylsulfate;
TES : Distearyl hydroxyethyl methyl ammonium methylsulfate;
TEHT : Di(hydrogenated tallow-carboxyethyl)hydroxyethyl methyl ammonium methylsulfate; TEP : Di(palmiticcarboxyethyl)hydroxyethyl methyl ammonium methylsulfate;
DEEDMAC : Dimethylbis[2-[(1-oxooctadecyl)oxy]ethyl]ammonium chloride; and
DHT : Dihydrogenated tallowdimethylammonium chloride.
TEAQ : methyl bis-[ethyl (tallowoyl)]- 2-hydroxyethyl ammonium methyl sulphate.
Preferably the rinse conditioner has a pH of less than 7. More preferably the rinse conditioner has a pH of from 3 to 6.5.
Preferably the pH of the aqueous solution of step (i) is less than 7, more preferably from pH 3 to 6.5. This in use pH is provided by the rinse conditioner formulation. The in use pH can be measured for example by measuring an aqueous solution of the rinse conditioner dosed at 1 g/L.
Preferably the rinse conditioner used in step (i) comprises at most 1 % anionic surfactant. More preferably the rinse conditioner is free from anionic surfactant. Preferably the rinse conditioner used in step (i) comprises at most 1 % nonionic surfactant. More preferably the rinse conditioner is free from nonionic surfactant.
Main wash detergent
The main wash detergent formulation may be a powder, liquid or gel.
The main wash detergent formulation is preferably a non-phosphate laundry detergent formulation, i.e., contains less than 1 wt% of phosphate. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
Preferably the pH of the aqueous solution of step (iii) is from pH 7 to 1 1 . This in use pH is provided by the main wash detergent formulation. The in use pH can be measured for example by measuring an aqueous solution of the main wash detergent dosed at 1 g/L. Powder laundry detergent formulations are predominantly carbonate built, i.e. the weight% of sodium carbonate is greater than the weight % sum of other builder ingredient present, preferably the weight% level of other builder materials is less than 30%, more preferably less than 15 wt% of the weight% level of sodium carbonate. Powders, should preferably give an in use pH of from 9.5 to 1 1 . Liquid detergent formulations should preferably give an in use pH of from 7 to 9.
Preferably the main wash detergent formulation are powder laundry detergent formulations.
Preferably the main wash detergent formulations used in step (iii) comprises at most 1 % quaternary ammonium compounds. More preferably the main wash detergent is free from quaternary ammonium compounds.
The main wash detergent formulation may be present in a polvyinylalcohol pouch for ease of dispensing.
The main wash detergent formulation may contain non-ionic surfactant preferably wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0 to 0.12; Preferably the main wash detergent formulation contains from 0.002 to 0.2wt% of a subtilisin protease enzyme, preferably from 0.005 to 0.05 wt%;
Alkyl Ether Carboxylic acid
Alkyl Ether Carboxylic acid have the form: R-(OCH2CH2)n-OCH2-COOH, wherein R is saturated or mono-unsaturated alkyl chain and n is preferably greater than 4, preferably selected from 5 to 20, most preferably 10 to 20, even more preferably from 15 to 20.
Alkyl Ether Carboxylic acid may be used as salt version for example sodium salt, or amine salt. So for the avoidance of doubt, where the acid form of the alkyl ether carboxylic acid is stated, or depicted, it is also intended to include carboxylate salts of the acid form.
The alkyl chain is preferably selected from: oleyl, Palmitoleyl, CH3(CH2)9-; CH3(CH2)i CH3(CH2)ii-; CH3(CH2)i2-; CH3(CH2)i3-; CH3(CH2)i4-; CH3(CH2)i5-; CH3(CH2)i6-; and,
CH3(CH2)i7-. More preferably CH3(CH2)n-; CH3(CH2)i7- and oleyl ; most preferably
CH3(CH2)i7- and oleyl.
Alkyl ether carboxylic acid are available from Kao (Akypo ®), Huntsman (Empicol®) and Clariant (Emulsogen ®).
Alkyl ether carboxylic acids may be prepared by the modified Williamson synthesis:
R-(OCH2CH2)n-OH+ NaOH +CICH2COONa→
R-(OCH2CH2)n-OCH2COONa + NaCI + H20
An alternative is via on oxidation reaction with a Pt or Pd catalyst as described
DE3135946; DE2816127 and EP0304763.
For powders the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder.
Surfactants
The main wash detergent formulation comprises anionic charged surfactant (which includes a mixture of the same). Alkyl ether carboxylate are included as anionic charged surfactant. Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal or amine salts of fatty acids (soaps), organic sulphates and sulphonates having alkyi radicals containing from about 8 to about 22 carbon atoms, the term alkyi being used to include the alkyi portion of higher alkyi radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyi sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyi Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyi C10 to C15 benzene sulphonates; and sodium alkyi 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 alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; soaps; alkyi (preferably methyl) ester sulphonates, and mixtures thereof.
The most preferred anionic surfactants are selected from: linear alkyi benzene sulphonates; alkyi sulphates; soaps; alkyi ether sulphates and mixtures thereof. Preferably the alkyi ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably the linear alkyi benzene sulphonate is a sodium Cn to C15 alkyi benzene sulphonates (LAS). Preferably the alkyi sulphates is a linear or branched sodium C12 to Cie alkyi sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyi sulphate). Soaps are preferably C12 to C18 saturated fatty acids, preferably they are present at levels of less than 3wt% of the formulation.
In carbonate built powder detergent, it is preferable in the composition that LAS is the dominant anionic surfactant present. It is preferably that >80wt% of the anionic surfactant present is LAS.
In liquid detergents, it is preferably that >70wt% of the anionic surfactant are selected from LAS and SLES.
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 Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide.
Preferably the non-ionic surfactant is an alkyl ethoxylated non-ionic surfactant and is a Cs to Cie primary alcohol, most preferably a C12-C16 primary alcohol, with an average ethoxylation of 7EO to 9EO units.
Protease
Subtilisin protease enzymes (EC 3.4.21 .62) hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Subtilisin protease enzymes are members of the subtilase type serine proteases family.
The Serine protease families are described in the MEROPS peptidase database
(http://merops.sanger.ac.uk/). The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 4 (1991 ) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523. Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub-divisions, of which the Subtilisin family is one.
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B.
alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in (WO93/18140). Further proteases are described in: W092/19729, WO96/034946, WO98/201 15, WO98/201 16, WO99/01 1768, WO01/44452, WO03/006602, WO04/03186, WO04/041979, WO07/006305, W01 1/036263, W01 1/036264, especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN' numbering. More preferred the subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H 120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
The use of protease provides enhances cleaning in combination with the method.
For powder inclusion the protease enzyme is preferably granulated and post-dosed into the powder. Preferably the enzyme granules have a particle size smaller than 2 mm, as determined using graded sieves. Most preferably the enzyme granules have a particle size from 0.2 to 1.5mm as determined using graded sieves.
Subtilisin are commercially available, for example, from Novozymes™ and Genencor™
For powders the alkyl ether carboxylic acid dispersants is preferably added to the slurry before granulation of the detergent powder. Alternatively, it may be separately granulated and post-dosed or sprayed onto the finished powder. Builders or Complexinq Agents
The main wash formulation preferably contains a builder or complexing agent. Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials 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. The main wash formulation 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. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
Zeolite and carbonate (including bicarbonate and sesquicarbonate) are preferred builders for powder detergents. The main wash formulation 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 5%wt. Aluminosilicates are materials having the general formula: 0.8-1.5 M20. AI2O3. 0.8-6 Si02 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 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Alternatively, or additionally to the aluminosilicate builders, other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) may be present.
Spray drying of the powder detergent is preferred.
Fluorescent Agent
The main wash formulation 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. 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]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.
It is preferred that the main wash aqueous solution used in the method has a fluorescer present. When 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.
Perfume
Preferably the rinse conditioner and main wash formulation both comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. It is commonplace for a plurality of perfume components to be present in a formulation. In the 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. Encapsulated perfume may be used. In perfume mixtures preferably 15 to 25 wt% are top notes. 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 cleaning and whiteness benefit of the invention.
Polymers
The main wash formulation may comprise one or more further polymers. Examples are carboxymethylcellulose, ethoxylated polyethyleneimine (EPEI), polymeric ester of aromatic dicarboxylic acids, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. EPEI is preferably a base (unreacted) polyethylene imine of 400 to 1200 molecular weight that has been ethoxylated with 10 to 30 mole equivalent of ethylene oxide per N-H in the a base (unreacted) polyethylene imine.
Further Enzymes
One or more further enzymes are preferred present in main wash formulation and when practicing a method of the invention.
Preferably the level of each further enzyme in the main wash formulation of the invention is from 0.0001 wt% to 0.1 wt% protein.
The further enzyme is preferably selected from: amylases, Mannanases, lipases; and, cellulases, most preferably amylases and lipases. Suitable lipases include those sold under the tradenames lipex®, Lipoclean® and Lipolex® by Novozymes, Bagsvaerd Denmark.
Any enzyme present in the main wash formulation 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.
Shading Dyes
Shading dyes are preferably present in the main wash formulation 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 2009/141 173 (Unilever), WO 2010/099997 (Unilever), WO 2010/102861 (Unilever), WO 2010/148624 (Unilever), WO2008/087497 (P&G), WO201 1/01 1799 (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. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497. Preferred examples of thiophene dyes are shown below:
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 1 1 , 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.. An example of an 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: X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5; X4 is selected from: -H; -CH3; -C2H5; -OCH3; and, -OC2H5;
Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(0)CH3; and, C(0)OCH3.
The shading dye is present 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 dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.
For ease of use it is preferred if the carbonate built powder detergent formulations are present in 0.5 to 5kg packs.
Experimental
Example 1 :
The following powder formulation was produced:
Ingredient Weight%
Sodium LAS 8.0
Sodium Silicate 7.1
Light soda ash 22.9
Sodium sulphate 59.4
Sokalan CP5 (BASF) 0.4
Sodium carboxy methyl cellulose 0.1
Fluorescer (Tinopal CBSx ex BASF) 0.02
moisture remainder The following rinse conditioner formulation was produced:
Eight, 5 x 5cm, white knitted cotton pieces were agitated in 800ml of 26° French Hard water at 25°C for 1 hour in a tergotometer (200 rpm) this provide control fabric. Eight, 5 x 5cm, white knitted cotton pieces were agitated in 800 ml of 26° French Hard water containing 0.8 g/L of the rinse conditioner formulation at 25°C for 1 hour in a tergotometer (200rpm), this provided rinse conditioner treated fabric. The fabric was then dried in air for 24 hours. The powder detergent was used at 2g/L to wash the eight, 5 x 5cm, control white knitted cotton pieces in 800ml of 26 French Hard water at 37.5°C for 1 hour in a tergotometer (200rpm). 0.04g/L of 100% compressed Carbon Black (Alfa Aesur) was added to the wash liquor, alongside 1/3rd sheet/L of an SBL2004 soil sheet cut into 20 equal sized pieces. This simulates oily soil in the wash and deposition of carbon based particulates. Following the wash the swatches are rinsed in 400ml 26 26 French Hard water and dried in air. The colour of the cloth was measured using a reflectometer and expressed as the CIE L*a*b* values. The experiment was repeated with using the rinse conditioner treated fabrics. The entire experiment was then repeated but with the addition of 0.2g/L of alkyl ether carboxylate (oleyl, 10EO) to the main wash solution.
The results are summarised in the table below
In the main wash control washed clothes, the rinse conditioner treated cloths were dirtier (L*=71.5) than the control (L*=73.6). However, in the main wash with alkyl ether carboxylate washed clothes the clothes treated with rinse conditioner were cleaner (L*=81.0) than the control (L*=77.2).
Treatment with rinse conditioner then a main wash with alkyl ether carboxylate provides the best cleaning, as evidenced by the greatest L* value (81.0).
Example 2
The experiment of example 1 was repeated. In the experiment, no prior rinse step was conducted. The fabric was washed in the powder formulation plus or minus the addition of 0.2g/L of alkyl ether carboxylate (oleyl, 10EO) to the wash solution and with the powder formulation and rinse conditioner added to the wash solution again plus or minus the addition of 0.2g/L of alkyl ether carboxylate (oleyl, 10EO).
The results are shown in the table below
For use of the main wash detergent alone, there is good agreement with the results of experiment 1 and experiment 2, with L* values of 73.6 and 73.3 which are within the 95% confidence limits.
This is also true for the main wash detergent with alkyl ether carboxylate, with L* of 77.2 and 76.6 for experiment 1 and experiment 2 respectively, again with the 95% confidence limits. When the main wash detergent and rinse conditioner are used together in a method that combines the rinse conditioner with quaternary ammonium compound and main wash detergent in the same step the L* is 74.5 and increases to 77.2 on further addition of alkyl ether carboxylate. The benefit of alkyl ether carboxylate for main wash detergent alone is 76.6-73.3 = 3.3 and for main wash detergent with rinse conditioner in the same step 77.2- 74.5 = 2.7. There is no additional advantage to using alkyl ether carboxylate in the method that combines the main wash detergent and rinse conditioner in the same step. This is in contrast to example 1 where increased performance is seen when the rinse conditioner and main wash detergent are used sequentially.

Claims

A wash method, the wash method comprising the sequential steps of:
(i) agitating a textile garment in an aqueous solution of from 0.5 to 10g/L of a rinse conditioner, wherein the rinse conditioner comprises from 1 to 25 wt% of a quaternary ammonium compound wherein in step (i) the quaternary ammonium compound has the general formula (I):
[N+(R1)(R2)(R3)(R4)]y X- (I), wherein:
Ri , R2, R3 and R4, are independently selected from a C1 -C30 hydrocarbon group, optionally containing a heteroatom or an ester or amide group; wherein at least one of Ri , R2, R3 and R4 are selected from C10 to C20 hydrocarbons group;
X is an anion; and,
y is the valence of X;
(ii) drying the textile garment;
(iii) agitating the textile garment in an aqueous solution of from 0.5 to 10g/L of a main wash detergent formulation comprising from 5 to 40 wt% of an anionic surfactant, the anionic surfactant providing from 0.02 to 1 g/L, of an alkyl ether carboxylic acid or carboxylate salt thereof of the following structure:
R-(OCH2CH2)n-OCH2-COOH, wherein R is a saturated or mono-unsaturated C10 to C18 alkyl chain and n is greater than 4, most preferably from 10 to 20; and,
(iv) optionally treating again with the rinse conditioner and drying the fabric.
A wash method according to claim 1 , wherein in step (iii) from 0.04 to 0.4g/L of the alkyl ether carboxylic acid or carboxylate salt thereof is present. A wash method according to claim 1 or 2, wherein R is selected from the group consisting of: lauryl; stearyl; and, oleyl alkyl chain and n is selected from 5 to 20.
A wash method according to any one of the preceding claims, wherein in step (i) 3 to 15 wt% of a quaternary ammonium compound is present.
A wash method according to any one of the preceding claims, wherein in step (iii) the main wash detergent formulation comprises from 10 to 20 wt% of an anionic surfactant.
A wash method according to any one of the preceding claims, wherein in step (iii) the main wash detergent formulation contains less than 1 wt% of phosphate.
A wash method according to any one of the preceding claims, wherein in step (iii) the main wash detergent formulation has a weight fraction of non-ionic surfactant/anionic surfactant of from 0 to 0.3.
A wash method according to any one of the preceding claims, wherein in step (iii) the anionic surfactant, other than the alkyl ether carboxylic acid or carboxylate salt thereof, is selected from: linear alkyl benzene sulphonates; alkyl sulphates; soaps; alkyl ether sulphates; and, mixtures thereof.
A wash method according to any one of the preceding claims, wherein in step (iii) the main wash detergent formulation comprises from 0.002 to 0.2wt% of a subtilisin protease enzyme.
A wash method according to any one of the preceding claims, wherein the pH of the aqueous solution of step (i) is less than 7, more preferably from pH 3 to 6.5, wherein said in use pH is provided by the rinse conditioner formulation.
A wash method according to any one of the preceding claims, wherein the pH of the aqueous solution of step (iii) is from pH 7 to 1 1 , wherein said in use pH is provided by the main wash detergent formulation.
2. A wash method according to any one of the preceding claims, wherein the rinse conditioner used in step (i) comprises at most 1 % anionic surfactant, preferably the rinse conditioner is free from anionic surfactant.
3. A wash method according to any one of the preceding claims, wherein the rinse
conditioner used in step (i) comprises at most 1 % nonionic surfactant, preferably the rinse conditioner is free from nonionic surfactant.
4. A wash method according to any one of the preceding claims, wherein the main wash detergent formulations used in step (iii) comprises at most 1 % quaternary ammonium compounds, preferably the main wash detergent is free from quaternary ammonium compounds.
EP17776999.9A 2016-09-27 2017-09-25 Domestic laundering method Active EP3519542B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16190945 2016-09-27
PCT/EP2017/074236 WO2018060139A1 (en) 2016-09-27 2017-09-25 Domestic laundering method

Publications (2)

Publication Number Publication Date
EP3519542A1 true EP3519542A1 (en) 2019-08-07
EP3519542B1 EP3519542B1 (en) 2020-02-19

Family

ID=57018034

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17776999.9A Active EP3519542B1 (en) 2016-09-27 2017-09-25 Domestic laundering method

Country Status (7)

Country Link
EP (1) EP3519542B1 (en)
CN (1) CN109790491B (en)
AR (1) AR109557A1 (en)
BR (1) BR112019006017A2 (en)
PH (1) PH12019500526B1 (en)
WO (1) WO2018060139A1 (en)
ZA (1) ZA201901996B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023012093A1 (en) 2021-08-05 2023-02-09 Unilever Ip Holdings B.V. Method
WO2025045963A1 (en) * 2023-08-30 2025-03-06 Unilever Ip Holdings B.V. Solid laundry composition

Family Cites Families (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3741911A (en) 1970-12-21 1973-06-26 Hart Chemical Ltd Phosphate-free detergent composition
JPS53141218A (en) 1977-05-16 1978-12-08 Kao Corp Oxidation of non-ionic surfactants
DE3135946A1 (en) 1981-09-10 1983-03-24 Bayer Ag, 5090 Leverkusen Process for preparing alkoxyacetic acids
NL8400706A (en) 1984-03-05 1985-10-01 Chem Y LAUNDRY DETERGENT.
DE3728222A1 (en) 1987-08-24 1989-03-09 Henkel Kgaa METHOD FOR THE PRODUCTION OF ETHERCARBONIC ACIDS
DK6488D0 (en) 1988-01-07 1988-01-07 Novo Industri As ENZYMES
US5269960A (en) 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
CA2001927C (en) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
EP0511456A1 (en) 1991-04-30 1992-11-04 The Procter & Gamble Company Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
CZ285148B6 (en) 1991-04-30 1999-05-12 The Procter And Gamble Company Liquid detergent mixture
ES2121014T3 (en) 1991-05-01 1998-11-16 Novo Nordisk As STABILIZED ENZYMES AND DETERGENT COMPOSITIONS.
DK28792D0 (en) 1992-03-04 1992-03-04 Novo Nordisk As NEW ENZYM
ATE429490T1 (en) 1995-05-05 2009-05-15 Novozymes As PROTEASE VARIANTS AND COMPOUNDS
GB2309706B (en) * 1996-01-31 2000-02-09 Reckitt & Colman Inc Liquid detergent composition comprising quaternary ammonium surfactant having germicidal properties
EP0932667B1 (en) 1996-11-04 2008-10-01 Novozymes A/S Subtilase variants and compositions
JP4044143B2 (en) 1996-11-04 2008-02-06 ノボザイムス アクティーゼルスカブ Subtilase variants and compositions
BR9811248B1 (en) 1997-08-29 2011-10-04 subtilase enzyme variant derived from an originating subtilase selected from subgroup i-s1 or subgroup i-s2, said variant having improved detergent wash performance compared to native subtilase, isolated dna sequence, vector expression, microbial host cell, process for producing a variant, composition, use of a subtilase variant.
GB2338242A (en) * 1998-06-10 1999-12-15 Reckitt & Colman Inc Germicidal laundry detergent
EP1244779B1 (en) 1999-12-15 2014-05-07 Novozymes A/S Subtilase variants having an improved wash performance on egg stains
DK200101090A (en) 2001-07-12 2001-08-16 Novozymes As Subtilase variants
DE10162728A1 (en) 2001-12-20 2003-07-10 Henkel Kgaa New alkaline protease from Bacillus gibsonii (DSM 14393) and washing and cleaning agents containing this new alkaline protease
EP1520017A2 (en) 2002-06-26 2005-04-06 Novozymes A/S Subtilases and subtilase variants having altered immunogenicity
TWI319007B (en) 2002-11-06 2010-01-01 Novozymes As Subtilase variants
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
US20080034511A1 (en) 2004-09-23 2008-02-14 Batchelor Stephen N Laundry Treatment Compositions
GB0421145D0 (en) 2004-09-23 2004-10-27 Unilever Plc Laundry treatment compositions
DE102004052007B4 (en) 2004-10-25 2007-12-06 Müller Weingarten AG Drive system of a forming press
EP2385111B1 (en) 2005-07-08 2016-09-07 Novozymes A/S Subtilase variants
PL1945747T3 (en) 2006-08-10 2010-02-26 Unilever Nv Shading composition
ATE486927T1 (en) 2007-01-19 2010-11-15 Procter & Gamble LAUNDRY CARE WITH WHITE TONER FOR CELLULOSE-CONTAINING SUBSTRATES
MY149525A (en) 2007-05-18 2013-09-13 Unilever Plc Triphenodioxazine dyes
DE102007038031A1 (en) 2007-08-10 2009-06-04 Henkel Ag & Co. Kgaa Agents containing proteases
BRPI0910682B1 (en) 2008-05-02 2020-09-24 Unilever N.V. TONING COLORING GRANULES THAT PRODUCE LESS STAINS, AND GRANULAR DETERGENT COMPOSITION FOR WASHING CLOTHES
BRPI0912868B1 (en) 2008-05-20 2020-10-27 Unilever N.V. composition of treatment for washing and home method for textile treatment
WO2010099997A1 (en) 2009-03-05 2010-09-10 Unilever Plc Dye radical initiators
ES2435470T3 (en) 2009-03-12 2013-12-19 Unilever Nv Dye polymer formulations
WO2010148624A1 (en) 2009-06-26 2010-12-29 Unilever Plc Dye polymers
CN102648277B (en) 2009-09-25 2015-05-20 诺维信公司 Use of protease variants
CN102648273B (en) 2009-09-25 2017-04-26 诺维信公司 Subtilase variants
WO2012054058A1 (en) 2010-10-22 2012-04-26 The Procter & Gamble Company Bis-azo colorants for use as bluing agents
US20120101018A1 (en) 2010-10-22 2012-04-26 Gregory Scot Miracle Bis-azo colorants for use as bluing agents
WO2010151906A2 (en) 2010-10-22 2010-12-29 Milliken & Company Bis-azo colorants for use as bluing agents
WO2011011799A2 (en) 2010-11-12 2011-01-27 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
EP2476743B1 (en) 2011-04-04 2013-04-24 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Method of laundering fabric
ES2622374T3 (en) 2011-12-12 2017-07-06 Unilever N.V. Compositions for washing clothes
WO2013087285A1 (en) * 2011-12-12 2013-06-20 Unilever Plc Laundry compositions and uses
WO2013142495A1 (en) 2012-03-19 2013-09-26 Milliken & Company Carboxylate dyes
EP2834340B1 (en) 2012-04-03 2016-06-29 The Procter and Gamble Company Laundry detergent composition comprising water-soluble phthalocyanine compound
DE102013218614A1 (en) 2013-09-17 2015-03-19 Henkel Ag & Co. Kgaa Detergent containing ether carboxylates

Also Published As

Publication number Publication date
CN109790491B (en) 2021-02-23
ZA201901996B (en) 2020-07-29
CN109790491A (en) 2019-05-21
AR109557A1 (en) 2018-12-19
EP3519542B1 (en) 2020-02-19
BR112019006017A2 (en) 2019-06-18
PH12019500526B1 (en) 2022-01-12
WO2018060139A1 (en) 2018-04-05
PH12019500526A1 (en) 2020-02-24

Similar Documents

Publication Publication Date Title
EP3356505B1 (en) Laundry detergent composition
EP3294852B1 (en) Laundry detergent composition
EP3356503B1 (en) Liquid laundry detergent composition
EP3519542B1 (en) Domestic laundering method
EP3303535B1 (en) Laundry detergent composition
EP3303537B1 (en) Laundry detergent composition
EP3303536B1 (en) Laundry detergent composition
BR112018016674A2 (en) laundry detergent composition and household method of treating a fabric

Legal Events

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

Free format text: STATUS: UNKNOWN

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: 20190315

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: 20191106

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: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017012068

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1234967

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200315

REG Reference to a national code

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: 20200219

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: 20200519

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: 20200219

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: 20200219

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: 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: 20200219

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: 20200219

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: 20200219

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: 20200519

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: 20200520

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: 20200619

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: 20200219

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

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: 20200219

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: 20200219

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: 20200219

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: 20200219

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: 20200712

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: 20200219

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: 20200219

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: 20200219

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: 20200219

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1234967

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200219

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602017012068

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20201117

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

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: 20200219

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: 20200219

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: 20200219

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

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20200930

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: 20200925

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602017012068

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

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

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: 20200930

Ref country code: BE

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

Effective date: 20200930

Ref country code: LI

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

Effective date: 20200930

Ref country code: IE

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

Effective date: 20200925

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: UNILEVER GLOBAL IP LIMITED

Owner name: UNILEVER IP HOLDINGS B.V.

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: 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: 20200219

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: 20200219

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: 20200219

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: 20200219

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: 20200219

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602017012068

Country of ref document: DE

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

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

Effective date: 20230428

27O Opposition rejected

Effective date: 20221208

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: 20200219

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

Ref country code: DE

Payment date: 20240918

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: 20240920

Year of fee payment: 8

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

Ref country code: FR

Payment date: 20240925

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: 20240916

Year of fee payment: 8