EP3555255B1 - Laundry detergent composition - Google Patents

Laundry detergent composition Download PDF

Info

Publication number
EP3555255B1
EP3555255B1 EP17793644.0A EP17793644A EP3555255B1 EP 3555255 B1 EP3555255 B1 EP 3555255B1 EP 17793644 A EP17793644 A EP 17793644A EP 3555255 B1 EP3555255 B1 EP 3555255B1
Authority
EP
European Patent Office
Prior art keywords
anionic surfactant
laundry detergent
detergent composition
surfactant
carboxylic acid
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
EP17793644.0A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3555255A1 (en
Inventor
Stephen Norman Batchelor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP3555255A1 publication Critical patent/EP3555255A1/en
Application granted granted Critical
Publication of EP3555255B1 publication Critical patent/EP3555255B1/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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the present invention provides an effective surfactant formulation for use in domestic laundry.
  • Aqueous domestic laundry liquid formulations containing lauryl ether sulfate in combination with another type of anionic surfactant as the main surfactants are ubiquitous.
  • the second anionic surfactant is typically linear alkyl benzene sulfonate. It is desirous that the surfactants fully dissolve in the water, to provide an aqueous solution of optical clarity; to facilitate this clarity hydrotropes are added. Effective binary anionic surfactant systems that fully dissolve in water without the need for an additional hydrotropes are required.
  • hydrotropes include ethylene glycol, 1,3 propanediol, 1,2 propanediol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 2,3-butane diol, 1,3 butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol formal dipropylene glycol, polypropylene glycol, dipropylene glycol n-butyl ether, sodium p-toluenesulfonate sodium xylene sulfonate and mixtures thereof.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • WO2014/060235 discloses a laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and to its use to soften fabrics.
  • the present invention provides an aqueous liquid laundry detergent composition comprising:
  • the further anionic surfactant(s) may serve to control foaming.
  • the present invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the clothes to be washed contain 0.1 to 2 wt% human sebum.
  • the surfactant used is preferably as preferred for the composition aspects of the present invention.
  • Domestic methods are preferably conducted in a domestic washing machine or by hand washing.
  • the temperature of the wash is preferably from 285 to 313K.
  • the main wash time is preferably 5 to 30 minutes.
  • the textile is preferably an item of clothing, bedding or table cloth.
  • Preferred items of clothing are cotton containing shirts, trousers, underwear and jumpers.
  • the aqueous liquid laundry detergent composition comprises less than or equal to 5 wt% (0 to 5 wt%), more preferably less than or equal to 0.2 wt% (0 to 0.2 wt%) of hydrotope selected from: ethylene glycol; 1,3 propanediol; 1,2 propanediol; tetramethylene glycol; pentamethylene glycol; hexamethylene glycol; 2,3-butane diol; 1,3 butanediol; diethylene glycol; triethylene glycol; polyethylene glycol; glycerol formal dipropylene glycol; polypropylene glycol; dipropylene glycol n-butyl ether; and, mixtures thereof.
  • hydrotope selected from: ethylene glycol; 1,3 propanediol; 1,2 propanediol; tetramethylene glycol; pentamethylene glycol; hexamethylene glycol; 2,3-butane diol; 1,3 butanediol; diethylene glyco
  • the hydrotope at the low level is selected from the group comprising: 1,2 propanediol; dipropylene glycol; polypropylene glycol; 2,3- butane diol; dipropylene glycol n-butyl ether; and, mixtures thereof.
  • the surfactants of invention are preferably non-amine neutralized.
  • Typical amine used to neutralise surfactants are alkyl ether carboxylic acid monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]- ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanol amine, isobutanolamine, monopentanol amine, I-amino-3-(2-methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)- 2-butanol, 6-amino-I-hexanol, heptaminol, isoetarine, norepinephrine, sphingosine, phenylpropanolamine and mixtures thereof.
  • the surfactants of invention are preferably neutralized with an aqueous solution of sodium hydroxide.
  • the surfactants are made from natural or synthetically derived chemicals, preferably they are naturally derived, most preferably the alkyl chains are obtained from renewable natural sources.
  • Weights of anionic surfactants are calculated as their protonated form.
  • Weights of alkyl ether carboxylic acid are calculated as the protonated form, R 2 -(OCH 2 CH 2 ) n -OCH 2 COOH. They may be used as salt version for example sodium salt, or amine salt.
  • the integer n is the mole average of ethoxylation per mole of surfactant.
  • the alkyl chain may be linear or branched, preferably it is linear.
  • the alkyl chain may be aliphatic or contain one cis or trans double bond.
  • the alkyl chain is preferably selected from CH 3 (CH 2 ) 11 , CH 3 (CH 2 ) 13 , CH3(CH 2 ) 15 , CH 3 (CH 2 ) 17 .
  • the alkyl ether carboxylic acid is most preferably selected from the structure: CH 3 (CH 2 ) 15 (OCH 2 CH 2 ) 20 OCH 2 COOH; and, CH 3 (CH 2 ) 17 (OCH 2 CH 2 ) 20 OCH 2 COOH.
  • Alkyl ether carboxylic acid are available from Kao (Akypo®), Huntsman (Empicol®) and Clariant (Emulsogen®).
  • Kao Alkypo®
  • Huntsman Empicol®
  • Clariant Clariant
  • the sodium salt of the alkyl ether carboxylate is most preferred.
  • AEC incorporation potentates the Ca and Mg salts of free fatty acids found in human sebum on clothes, converting them to useful soap surfactant. This allows use of less surfactant in the laundry liquid detergent for the same general detergency.
  • Palmitic and sapienic acid are particularly useful components of human sebum.
  • Weights of lauryl ether sulfate are calculated as the protonated form.
  • the average number of moles of ethoxylation per mole of surfactant is preferably 1 to 4, most preferably 2.5 to 3.5.
  • the sodium salt of the lauryl ether sulfate is preferred.
  • the non-ionic surfactant is preferably an ethoxylated alcohol non-ionic surfactant, preferably selected from: C10 to C16 primary and secondary aliphatic alcohols ethoxylated with an average of from 6 to 10 moles of ethylene oxide per mole of alcohol, most preferably a C12 to C15 primary aliphatic alcohol with 7 to 9 moles of ethylene oxide per mole of alcohol, wherein the weight fraction of ethoxylated alcohol non-ionic surfactant/ (lauryl ether sulfate anionic surfactant + alkyl ether carboxylic acid anionic surfactant) is from 0 to 0.4, preferably 0 to 0.2;
  • the alkyl chain is linear.
  • the aqueous liquid laundry detergent may comprises from 0 to 4 wt% of further surfactants, for example those described in " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996 ).
  • Suitable further anionic detergent compounds are; alkyl sulphates, especially those obtained by sulphating linear or branched C 8 to C 18 alcohols; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof. Soaps are particularly preferred, preferably from 0.5 to 2wt%.
  • Linear alkyl benzene sulphonates are preferably present in the aqueous liquid laundry detergent composition at a level from 0 to 1 wt% and ideally the composition is substantially devoid of linear alkyl benzene sulfonate.
  • the alkoxylated polyethyelene imine comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation.
  • Such materials may be represented as PEI(X)YAO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of alkoxylation (AO) per available NH in the unsubstituted polyethyleneimine backbone.
  • Y is preferably from 7 to 40 more preferably it is in the range of 16 to 26, most preferably 18 to 22.
  • X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
  • the alkoxylation is preferably selected from ethoxylation or propoxylation, or a combination of the two, Ethoxylation is most preferred.
  • the alkoxy chains may be capped with groups selected from: H; CH 3 ; SO 3 - ; CH 2 COO - ; PO 3 2- ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate, most preferably H.
  • alkoxylated PEI is PEI(600)20EO.
  • Terephthalate Polyester Soil Release Polymer comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), as described in WO2009/153184 , EP2692842 and WO2014/019903 .
  • Terephthalate Polyester Soil Release Polymer examples include the REPEL-O-TEX® line of polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2.
  • Other suitable soil release polymers include TexCare® polymers, including TexCare® SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare® SRN-300, and TexCare® SRN-325, all supplied by Clariant.
  • Preferred structure are -[(Z) a -O-OC-Ar-CO-] b and (Z) a -O-OC-[Ar-CO-O-C 3 H 6 -O-OC] b -Ar-COO-(Z) a , where Ar is selected from 1,4 substituted phenylene and 1,3 substituted phenylene substituted in the 5 position with a sulphonates (SO 3 - ) group; Z is selected from ethoxy;propoxy; and mixtures of ethoxy and propoxy; a is from 5 to 100 and b from 2 to 40.
  • C 3 H 6 is i-propyl.
  • the alkoxy chains are capped with groups selected from H; CH 3 ; SO 3 - ; CH 2 COO - ; PO 3 2- ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate.
  • the Terephthalate Polyester Soil Release Polymer is: wherein c is from 4 to 9; d is from 1 to 3; e is from 40 to 50.
  • the composition may comprise one or more further polymers.
  • examples are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Co-polymers as described in WO2014/082955 may be present.
  • Polymers present to prevent dye deposition may be present, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole). Such polymers are preferably present at levels of less then 0.5wt%.
  • composition is preferably devoid of silicone polymers and polymers bearing quaternised N groups.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALANTM.
  • the aqueous liquid laundry detergent formunation comprise from 0.1% to 2.0 wt% builder and sequesterant material. Citrate is most preferred.
  • the pH of the formulation is preferably from 6.5 to 8.5, most preferably 6.8 to 7.5. pH may be obtained by the addition of an alkali, such as NaOH or an amine.
  • 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.
  • Preferred mono-azo dyes contain a heterocyclic ring and are most preferably thiophene dyes.
  • Preferred examples of thiophene dyes are shown below: and,
  • 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.
  • 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 blue 101; 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.
  • proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred.
  • the term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng.
  • 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 subdivisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
  • 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 ).
  • proteases may be those described in WO92/175177 , WO01/016285 , WO02/026024 and WO02/016547 .
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270 , WO94/25583 and WO05/040372 , and the chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146 .
  • proteases are the variants described in: WO92/19729 , WO96/034946 , WO98/201 15 , WO98/201 16 , WO99/01 1768 , WO01/44452 , WO03/006602 , WO04/03186 , WO04/041979 , WO07/006305 , WO1 1/036263 , WO1 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.
  • 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, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
  • protease is a subtilisins (EC 3.4.21.62).
  • 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 ).
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B.
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
  • Maxatase® Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3®, FN4®, Excellase®, Opticlean® and Optimase® (Danisco/DuPont), AxapemTM (Gist-Brocases N.V.),
  • BLAP BLAP with S3T + V4I + V199M + V205I + L217D
  • BLAP X BLAP with S3T + V4I + V205I
  • BLAP F49 BLAP with S3T + V4I + A194P + V199M + V205I + L217D
  • 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 selected from: alpha-amylases; lipases; and, cellulases.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces ) , e.g. from H. lanuginosa ( T. lanuginosus ) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P.
  • lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 , and WO 00/60063 .
  • LipolaseTM and Lipolase UltraTM LipexTM and LipocleanTM (Novozymes A/S).
  • the method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • the method of the invention may be carried out in the presence of cutinase classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B . licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 .
  • amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
  • cellulases include CelluzymeTM, CarezymeTM, CellucleanTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
  • CellucleanTM is preferred.
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C . cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 .
  • Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
  • 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
  • alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains.
  • the alkyl groups are preferably linear or branched, most preferably linear.
  • 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.
  • 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.
  • 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
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-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' disulophonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2'disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • the total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt %, more preferably 0.005 to 2 wt %, most preferably 0.05 to 0.25 wt %.
  • the aqueous solution used in the method has a fluorescer present.
  • the fluorescer is present in the aqueous solution used in the method preferably in the range from 0.0001 g/l to 0.1 g/l, more 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 %, more preferably 0.05 to 0.5 wt%, most preferably from 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; Pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl an
  • Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press ; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand ; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
  • Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
  • perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (ie. those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0.
  • these materials have been called the "delayed blooming" perfume ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethy
  • 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 from the list given of delayed blooming perfumes given above present in the perfume.
  • perfumes with which the present invention can be applied are the socalled 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
  • 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.
  • indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
  • the at least 60 wt% containing composition comprises from 4 to 6 wt% of lauryl ether sulfate anionic surfactant with a mole average of 2.5 to 3.5 moles of ethoxylation per mole surfactant; from 4 to 6 wt% of an stearyl ether carboxylic acid anionic surfactant with a mole average of 15 to 20 moles of ethoxylation per mole surfactant; from 0 to 2 wt% of an C12 to C15 primary aliphatic alcohol with 7 to 9 moles of ethylene oxide per mole of alcohol non-ionic surfactant.
  • the liquid laundry detergent composition may be present in a water-soluble unit dose article.
  • the water-soluble unit dose article comprises at least one water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film.
  • the at least one compartment comprises the liquid laundry detergent composition.
  • the water-soluble film is sealed such that the liquid laundry detergent composition does not leak out of the compartment during storage.
  • the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
  • Aqueous laundry liquid detergent were made, as outlined in the table below.
  • the pH of the liquid was adjusted to 7.
  • the optical absorbance was measures in a 1cm cell at 470nm and is also reported in the table. Higher absorbance values indicate scattering effects dye to incomplete solubilisation of the surfactant mix.
  • Ref 1 Inv 1 Ref 2 Inv 2 Linear alkyl benzene sulfonate 5 4
  • the inventive formulation Inv 1 and Inv 2 containing the alkyl ether carboxylic acid have lower absorbance than the comparative reference formulations, indicating better solubilisation of the surfactant mix.

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)
EP17793644.0A 2016-12-15 2017-11-02 Laundry detergent composition Active EP3555255B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16204322 2016-12-15
PCT/EP2017/078016 WO2018108382A1 (en) 2016-12-15 2017-11-02 Laundry detergent composition

Publications (2)

Publication Number Publication Date
EP3555255A1 EP3555255A1 (en) 2019-10-23
EP3555255B1 true EP3555255B1 (en) 2020-06-24

Family

ID=57570203

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17793644.0A Active EP3555255B1 (en) 2016-12-15 2017-11-02 Laundry detergent composition

Country Status (6)

Country Link
EP (1) EP3555255B1 (zh)
CN (1) CN110023469A (zh)
AR (1) AR110513A1 (zh)
BR (1) BR112019011999B1 (zh)
WO (1) WO2018108382A1 (zh)
ZA (1) ZA201902425B (zh)

Family Cites Families (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296839A (zh) 1969-05-29 1972-11-22
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4760025A (en) 1984-05-29 1988-07-26 Genencor, Inc. Modified enzymes and methods for making same
EP0218272B1 (en) 1985-08-09 1992-03-18 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
US4810414A (en) 1986-08-29 1989-03-07 Novo Industri A/S Enzymatic detergent additive
NZ221627A (en) 1986-09-09 1993-04-28 Genencor Inc Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios
ATE125865T1 (de) 1987-08-28 1995-08-15 Novo Nordisk As Rekombinante humicola-lipase und verfahren zur herstellung von rekombinanten humicola-lipasen.
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
ATE129523T1 (de) 1988-01-07 1995-11-15 Novo Nordisk As Spezifische protease.
DK6488D0 (da) 1988-01-07 1988-01-07 Novo Industri As Enzymer
JP3079276B2 (ja) 1988-02-28 2000-08-21 天野製薬株式会社 組換え体ｄｎａ、それを含むシュードモナス属菌及びそれを用いたリパーゼの製造法
WO1989009259A1 (en) 1988-03-24 1989-10-05 Novo-Nordisk A/S A cellulase preparation
US5776757A (en) 1988-03-24 1998-07-07 Novo Nordisk A/S Fungal cellulase composition containing alkaline CMC-endoglucanase and essentially no cellobiohydrolase and method of making thereof
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
GB8915658D0 (en) 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
DK0493398T3 (da) 1989-08-25 2000-05-22 Henkel Research Corp Alkalisk, proteolytisk enzym og fremgangsmåde til fremstilling deraf
EP0528828B2 (de) 1990-04-14 1997-12-03 Genencor International GmbH Alkalische bacillus-lipasen, hierfür codierende dna-sequenzen sowie bacilli, die diese lipasen produzieren
ES2121786T3 (es) 1990-09-13 1998-12-16 Novo Nordisk As Variantes de lipasa.
DK58491D0 (da) 1991-04-03 1991-04-03 Novo Nordisk As Hidtil ukendte proteaser
EP0511456A1 (en) 1991-04-30 1992-11-04 The Procter & Gamble Company Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
ATE136055T1 (de) 1991-04-30 1996-04-15 Procter & Gamble Gerüstsubstanzhaltige flüssigwaschmittel mit borsäure-polyolkomplex zur ptoteolytischen enzyminhibierung
EP0583339B1 (en) 1991-05-01 1998-07-08 Novo Nordisk A/S Stabilized enzymes and detergent compositions
DK28792D0 (da) 1992-03-04 1992-03-04 Novo Nordisk As Nyt enzym
DK72992D0 (da) 1992-06-01 1992-06-01 Novo Nordisk As Enzym
DK88892D0 (da) 1992-07-06 1992-07-06 Novo Nordisk As Forbindelse
CA2138519C (en) 1993-04-27 2007-06-12 Jan Metske Van Der Laan New lipase variants for use in detergent applications
DK52393D0 (zh) 1993-05-05 1993-05-05 Novo Nordisk As
JP2859520B2 (ja) 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
KR100338786B1 (ko) 1993-10-13 2002-12-02 노보자임스 에이/에스 H2o2-안정한퍼록시다제변이체
AU8079794A (en) 1993-10-14 1995-05-04 Procter & Gamble Company, The Protease-containing cleaning compositions
JPH07143883A (ja) 1993-11-24 1995-06-06 Showa Denko Kk リパーゼ遺伝子及び変異体リパーゼ
AU1806795A (en) 1994-02-22 1995-09-04 Novo Nordisk A/S A method of preparing a variant of a lipolytic enzyme
AU2067795A (en) 1994-03-29 1995-10-17 Novo Nordisk A/S Alkaline bacillus amylase
CA2189441C (en) 1994-05-04 2009-06-30 Wolfgang Aehle Lipases with improved surfactant resistance
AU2884595A (en) 1994-06-20 1996-01-15 Unilever Plc Modified pseudomonas lipases and their use
WO1996000292A1 (en) 1994-06-23 1996-01-04 Unilever N.V. Modified pseudomonas lipases and their use
BE1008998A3 (fr) 1994-10-14 1996-10-01 Solvay Lipase, microorganisme la produisant, procede de preparation de cette lipase et utilisations de celle-ci.
WO1996013580A1 (en) 1994-10-26 1996-05-09 Novo Nordisk A/S An enzyme with lipolytic activity
JPH08228778A (ja) 1995-02-27 1996-09-10 Showa Denko Kk 新規なリパーゼ遺伝子及びそれを用いたリパーゼの製造方法
ATE315083T1 (de) 1995-03-17 2006-02-15 Novozymes As Neue endoglukanase
CN100387712C (zh) 1995-05-05 2008-05-14 诺沃奇梅兹有限公司 蛋白酶变体和组合物
CN1193346A (zh) 1995-07-14 1998-09-16 诺沃挪第克公司 一种具有脂解活性的修饰酶
ATE267248T1 (de) 1995-08-11 2004-06-15 Novozymes As Neuartige lipolytische enzyme
CN101085985B (zh) 1996-09-17 2012-05-16 诺沃奇梅兹有限公司 纤维素酶变体
CN1232384A (zh) 1996-10-08 1999-10-20 诺沃挪第克公司 作为染料前体的二氨基苯甲酸衍生物
EP2278001B1 (en) 1996-11-04 2013-10-23 Novozymes A/S Protease variants and compositions
EP0932667B1 (en) 1996-11-04 2008-10-01 Novozymes A/S Subtilase variants and compositions
JP5095884B2 (ja) 1997-08-29 2012-12-12 ノボザイムス アクティーゼルスカブ プロテアーゼ変異体及び組成物
MA25044A1 (fr) 1997-10-23 2000-10-01 Procter & Gamble Compositions de lavage contenant des variants de proteases multisubstituees.
US6939702B1 (en) 1999-03-31 2005-09-06 Novozymes A/S Lipase variant
CN1234854C (zh) 1999-03-31 2006-01-04 诺维信公司 具有碱性α－淀粉酶活性的多肽以及编码该多肽的核酸
NZ531394A (en) 1999-08-31 2005-10-28 Novozymes As Residual protease II (RPII) and variants thereof useful in detergent compositions
CN1415011B (zh) 1999-12-15 2010-12-08 诺沃奇梅兹有限公司 对蛋渍具有改进洗涤性能的枯草杆菌酶变体
CN1337553A (zh) 2000-08-05 2002-02-27 李海泉 地下观光游乐园
AU2001279614B2 (en) 2000-08-21 2006-08-17 Novozymes A/S Subtilase enzymes
DK200101090A (da) 2001-07-12 2001-08-16 Novozymes As Subtilase variants
DE10162728A1 (de) 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14393) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
US20060228791A1 (en) 2002-06-26 2006-10-12 Novozymes A/S Subtilases and subtilase variants having altered immunogenicity
TWI319007B (en) 2002-11-06 2010-01-01 Novozymes As Subtilase variants
JP4880469B2 (ja) 2003-10-23 2012-02-22 ノボザイムス アクティーゼルスカブ 洗剤中で改良された安定性を有するプロテアーゼ
BRPI0416797A (pt) 2003-11-19 2007-04-17 Genencor Int serina proteases, ácidos nucléicos codificando enzimas de serina e vetores e células hospedeiras incorporando as mesmas
EP1904628B1 (en) 2005-07-08 2011-10-19 Novozymes A/S Subtilase variants
ES2293826B1 (es) * 2006-06-07 2008-12-16 Kao Corporation S.A. Composicion detergente.
JP5122583B2 (ja) 2007-01-19 2013-01-16 ザ プロクター アンド ギャンブル カンパニー セルロース基材用増白剤を含む洗濯ケア組成物
DE102007038031A1 (de) 2007-08-10 2009-06-04 Henkel Ag & Co. Kgaa Mittel enthaltend Proteasen
BRPI0822220A2 (pt) 2008-01-04 2015-06-23 Procter & Gamble Composições contendo enzima e agente de matiz para tecidos
EP2085070A1 (en) 2008-01-11 2009-08-05 Procter & Gamble International Operations SA. Cleaning and/or treatment compositions
AR070498A1 (es) 2008-02-29 2010-04-07 Procter & Gamble Composicion detergente que comprende lipasa
CN101960007A (zh) 2008-02-29 2011-01-26 宝洁公司 包含脂肪酶的洗涤剂组合物
ES2720369T3 (es) 2008-06-06 2019-07-19 Procter & Gamble Composición detergente que comprende una variante de una xiloglucanasa de la familia 44
EP2300586B1 (en) 2008-06-16 2015-04-08 Unilever PLC Improvements relating to fabric cleaning
JP6204018B2 (ja) 2009-09-25 2017-09-27 ノボザイムス アクティーゼルスカブ プロテアーゼ変異体の使用
US20120172280A1 (en) 2009-09-25 2012-07-05 Novozymes A/S Protease Variants
MX2013006180A (es) * 2010-12-01 2013-07-15 Procter & Gamble Composiciones para el cuidado de tela.
CN103975049A (zh) * 2011-12-12 2014-08-06 荷兰联合利华有限公司 洗衣组合物
EP2791310B1 (en) 2011-12-12 2017-01-18 Unilever Plc. Laundry compositions
TR201900214T4 (tr) 2012-03-19 2019-02-21 Milliken & Co Karboksilat Boyalar
EP2692842B1 (en) 2012-07-31 2014-07-30 Unilever PLC Concentrated liquid detergent compositions
EP2880074B1 (en) 2012-07-31 2016-06-29 Unilever Plc. Alkaline liquid laundry detergent compositions comprising polyesters
ES2601135T3 (es) 2012-10-17 2017-02-14 Unilever N.V. Composiciones para lavado de ropa
US20150337241A1 (en) 2012-11-29 2015-11-26 Conopco, Inc. D/B/A Unilever Thickened aqueous detergent liquid
CN104194963B (zh) * 2014-09-19 2017-07-07 江苏万淇生物科技有限公司 无酶稳定剂的高浓缩含酶洗衣液
CN109072130B (zh) * 2015-05-27 2020-10-27 荷兰联合利华有限公司 洗衣洗涤剂组合物
WO2017162378A1 (en) * 2016-03-21 2017-09-28 Unilever Plc Laundry detergent composition

Non-Patent Citations (1)

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

Also Published As

Publication number Publication date
WO2018108382A1 (en) 2018-06-21
BR112019011999B1 (pt) 2022-11-08
BR112019011999A2 (pt) 2019-10-29
AR110513A1 (es) 2019-04-03
CN110023469A (zh) 2019-07-16
ZA201902425B (en) 2020-08-26
EP3555255A1 (en) 2019-10-23

Similar Documents

Publication Publication Date Title
EP3649222B1 (en) Whitening composition
EP3440170B1 (en) Laundry detergent composition
EP3307861B1 (en) Laundry detergent composition
EP3433346B1 (en) Laundry detergent composition
EP3440172B1 (en) Laundry detergent composition
EP3990604B1 (en) Detergent composition
EP3990603B1 (en) Detergent composition
EP3555255B1 (en) Laundry detergent composition
EP3417040B1 (en) Whitening composition
US20220372400A1 (en) Detergent composition
EP3313966B1 (en) Laundry detergent composition
EP3649221B1 (en) Laundry cleaning composition
EP3884022B1 (en) Detergent composition
EP3417039B1 (en) Whitening composition
US20220372397A1 (en) Detergent composition
WO2020104156A1 (en) Detergent composition

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: 20190404

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

INTG Intention to grant announced

Effective date: 20200207

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017018809

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1283900

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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

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: 20200624

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: 20200624

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: 20200924

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: 20200925

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: 20200624

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: 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: 20200624

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: 20200624

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: 20200924

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: 20200624

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200624

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1283900

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200624

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

Ref country code: AL

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

Effective date: 20200624

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: 20200624

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

Ref country code: PT

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

Effective date: 20201026

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: 20200624

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: 20200624

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: 20200624

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: 20200624

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: 20200624

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: 20200624

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: 20200624

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

Ref country code: IS

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

Effective date: 20201024

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: 20200624

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: 20200624

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017018809

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: 20200624

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210325

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: 20200624

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LU

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

Effective date: 20201102

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201130

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602017018809

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: 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: 20200624

Ref country code: LI

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

Effective date: 20201130

Ref country code: CH

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

Effective date: 20201130

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: 20201102

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: 20200624

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: 20200624

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: 20200624

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: 20201130

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

Ref country code: GB

Payment date: 20231123

Year of fee payment: 7

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

Ref country code: TR

Payment date: 20231030

Year of fee payment: 7

Ref country code: FR

Payment date: 20231120

Year of fee payment: 7

Ref country code: DE

Payment date: 20231121

Year of fee payment: 7