WO2009112298A1 - Laundry treatment composition comprising polymeric lubricants - Google Patents

Laundry treatment composition comprising polymeric lubricants Download PDF

Info

Publication number
WO2009112298A1
WO2009112298A1 PCT/EP2009/050700 EP2009050700W WO2009112298A1 WO 2009112298 A1 WO2009112298 A1 WO 2009112298A1 EP 2009050700 W EP2009050700 W EP 2009050700W WO 2009112298 A1 WO2009112298 A1 WO 2009112298A1
Authority
WO
WIPO (PCT)
Prior art keywords
laundry treatment
treatment composition
polyolefin
polyolefin particle
composition according
Prior art date
Application number
PCT/EP2009/050700
Other languages
French (fr)
Inventor
Stephen Normal Batchelor
Andrew Philip Parker
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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 N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to BRPI0909346A priority Critical patent/BRPI0909346A2/en
Priority to ES09719383T priority patent/ES2390112T3/en
Priority to EP09719383A priority patent/EP2252680B1/en
Priority to CN2009801087616A priority patent/CN101970632B/en
Publication of WO2009112298A1 publication Critical patent/WO2009112298A1/en
Priority to ZA2010/05759A priority patent/ZA201005759B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins

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)

Abstract

Wash added fabric care compositions including a polyolefin particle are described, more particularly granular detergent compositions including polyolefin particles. A method for applying these compositions during the wash cycle of a laundry process is also included.

Description

LAUNDRY TREATMENT COMPOSITION COMPRISING POLYMERIC LUBRICANTS
FIELD OF INVENTION
The present invention relates to wash added, fabric care compos itions and methods for us ing the same during the wash cycle of a consumer laundry proces s .
BACKGROUND
Coloured clothes are extremely popular with consumers. To remove dirt on washing, the clothes are vigorously agitated in water with a washing formulation. This process leads to damage on the surface of the clothes, which reduces their aesthetic appeal.
EP 1 478 720 (Procter & Gamble) discloses the use of dispersible polyolefin waxes in detergent formulations with mean particle sizes from 5nm to 5 microns.
SUMMARY OF INVENTION
We have found that using polyolefin particles larger than described in the prior art provide improved colour care. Further these larger polyolefin particles are easier to incorporate into a detergent composition because they do not need to be pre-dispersed before dosing.
In one aspect the present invention provides a granular laundry treatment composition containing less than 1 wt . % of phosphate comprising: (i) from 0.2 wt . % to 4 wt . % of a polyolefin particle, the polyolefin particle having a size in the range from 25 to 5000 microns;
(ii) from 2 to 70 wt . % of a surfactant; and, (iϋ) from 1 to 50 wt . % of a builder.
A second aspect of the invention provides a domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of from 1 to 20 g/1 of the composition of the first aspect; and, (ii) rinsing and drying the textile.
DETAILED DESCRIPTION OF THE INVENTION
The amount of components in the granular laundry treatment composition quoted herein are wt . % of total composition unless otherwise stated.
The polyolefin particle should not dissolve in water or surfactant solutions. Such that when lg/L of particles are placed into an aqueous solution containing 2g/L of sodium dodecyl sulphate at room temperature and shaken at 100 RPM on a rotator shaker at 293K for 2 hours, then removed from solution by filtering through a sieve or filter paper of appropriate size and dried. The weight of the particle removed is within 95 more preferably 99% of that added.
The polyolefin particle should have a weight average molecular weight in excess of 2000, more preferably in excess of 10000. The weight average molecular weight may be measured by vapour phase osmometry or cryoscopy.
The polyolefin particle has an acid number from about 0 to 200 mg/g KOH and preferably from about 0 to 4 mg/g KOH
(wherein the acid number indicates the mg of KOH needed to neutralize 1 g of polyolefin) . Preferably the particles are spherical or elliptical in cross-section.
Preferably the particles are white, such that when their colour is measured using a reflectometer (UV excluded) and expressed as CIE L*a*b* values, L*>70, a* is between -3 and +3 and b* is between 5 and -10.
The density of the particle is preferably 0.85 to 1.1 g/cm3, more preferably 0.95 to 1.05 g/cm3.
More preferably the polyolefin particle is selected from:
(a) polyethylenes :
Figure imgf000004_0001
(b) polypropylenes :
Figure imgf000004_0002
It is most preferred that the polyolefin particle is a polyethylene . The size of the polyolefin particle is measured using graded sieves and it is that that is retained or passes through such sieves .
The polyolefin particle is sized preferably from 50 to 2500 microns .
An advantage over the disclosure of EP 1 478 720 is that the use of a larger particle size provides ease of incorporation of the polyolefin particle into the composition, i.e., the particle may be added directly rather than via a suspension, dispersion, or an emulsion of polyolefin wax. Thus the granular laundry treatment composition can be provided by post-dosed addition of polyolefin particles. Another advantage is that larger particles are much less likely to become airborne during handling or sniffing and consequently less likely to be inhaled.
SURFACTANT
The composition comprises between 2 to 70 wt . % of a surfactant, most preferably 10 to 30 wt . % . In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "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. Preferably the surfactants used are saturated. Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are Ce to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl Cio to Ci5 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cu to Ci5 alkyl benzene sulphonates and sodium C12 to Cis alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .
Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C±β to Cis primary alcohol sulphate together with a C12 to Ci5 primary alcohol 3 to 7 EO ethoxylate .
The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt . % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5 wt . % to about 40 wt . % of the surfactant system.
BUILDERS OR COMPLEXING AGENTS
The composition comprises from 1 to 50 wt . % of a builder.
Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
It is preferred that when an insoluble inorganic builder, e.g., zeolite, is used the size is in the range 0.1 to 10 microns (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex Malvern™) . 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-O, 384, 070.
The composition may also contain 0-50 wt . % 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 (carbonate (including bicarbonate and sesquicarbonate) are preferred builders.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt . % . Aluminosilicates are materials having the general formula: 0 . 8 - 1 . 5 M2O . Al2O3 . 0 . 8 - 6 S iO2
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 SiO2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to aluminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term λphosphate' embraces diphosphate, triphosphate, and phosphonate species. However, the formulation comprises less than 1 wt . % of such phosphate builders. Preferably the laundry detergent formulation is free from phosphate builders.
Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) .
We have also found that the presence of an inorganic builder in particular a zeolite, (insoluble inorganic particulates) contributes to the abrasion of fabrics under wash conditions. The use of the larger polyolefin particles ameliorate this problem. SHADING AGENT
The granular laundry treatment composition preferably comprises a blue or violet shading agent in the range from 0.0001 to 0.01 wt . % . The shading agents reduce the perception of damage to many coloured garments and increase whiteness of white garments.
The shading agents are preferably selected from blue and violet dyes of the solvent disperse basic, direct and acid type listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists 2002) .
Preferably a direct violet or direct blue dyes is present. Preferably the dyes are bis-azo, tris-azo dyes or triphendioxazine dye. The carcinogenic benzidene based dyes are not preferred.
Bis-azo copper containing dyes such as direct violet 66 may be used.
The most preferred bis-azo dyes have the following structure :
Figure imgf000010_0001
or
R^2
Figure imgf000011_0001
wherein : ring D and E may be independently naphthyl or phenyl as shown;
Ri is selected from: hydrogen and Cl-C4-alkyl, preferably hydrogen;
R2 is selected from: hydrogen, Cl-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
R3 and R4 are independently selected from: hydrogen and Cl- C4-alkyl, preferably hydrogen or methyl;
X and Y are independently selected from: hydrogen, C1-C4- alkyl and Cl-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
Preferred bis-azo dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
Preferred solvent and disperse dyes, are selected from, mono-azo or anthraquinone dyes, most preferably, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
A preferred pigment is pigment violet 23.
ENZYMES
The granular laundry treatment composition preferably comprises one or more enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, - lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with amylase. When present in a cleaning composition, the aforementioned additional enzymes may be present at levels from about 0.00001 wt . % to about 2 wt. %, from about 0.0001 wt . % to about 1 wt . % or even from about 0.001 wt .% to about 0.5 wt . % enzyme protein by weight of the composition.
Preferred enzymes are cellulases. FLUORESCENT AGENT
The composition preferably comprises a fluorescent agent (optical brightener) . Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt. %, more preferably 0.01 to 0.1 wt . % . Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2- (4-styryl-3- sulfophenyl) -2H-napthol [ 1 , 2-d] trazole, disodium 4,4'- bis { [ (4-anilino-6- (N methyl-N-2 hydroxyethyl) amino 1,3,5- triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium
4, 4 ' -bis { [ (4-anilino-6-morpholino-l, 3,5-triazin-2-yl) ] amino } stilbene-2-2' disulfonate, and disodium 4, 4 '-bis (2- sulfoslyryl) biphenyl .
PERFUME
Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%. 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.
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 fabric care benefit of the invention.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
POLYMERS
The composition may comprise one or more polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. Polymers present to prevent dye deposition, for example poly (vinylpyrrolidone) , poly (vinylpyridine-N-oxide) , and poly (vinylimidazole) , are preferably absent from the formulation .
Experimental
Example 1
Three knitted cotton fabric swatches (20 by 20 cm) dyed with Vat Blue 4 were washed in a compartment of a Quickwash Plus ™ fabric testing system (SDL international) . In a separate compartment equivalent knitted cotton swatches were placed, but these were dyes with Reactive Orange 16. The machine was filled with 3.5 litres of 26° French Hard water and 24.5 g of Persil Colour Powder (ex UK) a Las/Non-ionic surfactant powder built with zeolite and carbonate. To this was added 0.5g of antifoam. The wash took 15 minutes, and following this the machine was drained, spun, and then three 90 second rinses performed, draining and spinning after each. Following the wash the fabric was tumble dried. The procedure was repeated 5 times. The whole experiment was then repeated but with the addition of lg/L of various additives .
Following the washes the reflectances of the VAT Blue cloths at 430nm and the Reactive Orange cloths at 650nm were measured on a Murakami Goniospectrophotometer with an incident angle of 65° and a measurement angle of 55°. The reflectance of the new cloths was 27.20 for the Vat Blue and 65.13 for the reactive Orange. The reflectance was compare to the reflectance of new unwashed fabric, and expressed as ΔR = I R (new) - R (washed) | . The ΔR (powder control) for Vat Blue was 6.06 and for Reactive Orange was 5.36. In the results the average ΔR between the blue and orange cloths is given to 1 decimal place.
The results are shown in table 1.
Table 1
Figure imgf000017_0001
particle size measured by SEM of commercial sample use in experiment .
The large organic polymer particles maintain the cloth closer to the new, as indicated by smaller ΔRaverage values. Example 2
The experiment of example 1 was repeated using different levels of Licowax PE520P. The results are shown in the table below for the Vat Blue dyes cloth.
Figure imgf000018_0001
The polyethylene particles are effective across a wide range of dosages.
- I i
Example 3
Exemplary Granular Laundry Formulations A, B, C, D
Figure imgf000019_0001
Enzyme levels are given as percent pure enzyme. Levels of direct violet 9, solvent violet 13 and Sulfonated Zn Pthalocyanine photobleach are given as pure dye. NI (7EO) refers to R- (OCH2CH2) n0H, where R is an alkyl chain of C12 to C15, and n is 7.
The formulations are prepared by adding direct violet 9, acid violet 7 and the Sulfonated Zn Pthalocyanine photobleach into the slurry which is then spray dried. Alternatively, the dyes and photobleach may be added via post-dosed MgSO4 granules.
The solvent violet 13 was dissolved in non-ionic surfactant (7EO) and granulated onto bentonite clay, to give a granule containing 0.2 wt . % dye. This was post-dosed to the formulation .
The Licowax PE520P particles were post dosed to the formulation .

Claims

1. A granular laundry treatment composition containing less than 1 wt . % of phosphate comprising:
(i) from 0.2 wt % to 4 wt . % of a polyolefin particle, the polyolefin particle having a size in the range from 25 to 5000 microns; (ii) from 2 to 70 wt . % of a surfactant; and,
(iii) from 1 to 50 wt . % of a builder.
2. A granular laundry treatment composition according to claim 1, wherein the polyolefin particle has a size in the range from 50 to 2500 microns.
3. A granular laundry treatment composition according to claim 1 or claim 2, wherein the polyolefin particle is polyethylene .
4. A granular laundry treatment composition according to any preceding claim, wherein the polyolefin particle has been added to the laundry treatment composition as post dosed particles of polyolefin particle.
5. A granular laundry treatment composition according to any preceding claim, wherein the builder comprises zeolite, the zeolite having a size in the range from 0.1 to 10 microns.
6. A granular laundry treatment composition according to any preceding claim, wherein the laundry treatment composition comprises a blue or violet shading agent in the range from 0.0001 to 0.01 wt . % .
7. A granular laundry treatment composition according to any preceding claim, wherein the laundry treatment composition comprises one or more enzymes, at a level of from about 0.00001 wt . % to about 2 wt.%, preferably the enzyme is a cellulase.
8. A domestic method of treating a textile, comprising the steps of:
(i) treating a textile with an aqueous solution of from 1 to 20 g/1 of the composition of any one of claims 1 to 7; and, (ii) rinsing and drying the textile.
PCT/EP2009/050700 2008-03-14 2009-01-22 Laundry treatment composition comprising polymeric lubricants WO2009112298A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BRPI0909346A BRPI0909346A2 (en) 2008-03-14 2009-01-22 granular composition of polyolefin particle-containing tissue treatment, and domestic method of tissue treatment
ES09719383T ES2390112T3 (en) 2008-03-14 2009-01-22 Washing treatment composition comprising polymeric lubricants
EP09719383A EP2252680B1 (en) 2008-03-14 2009-01-22 Laundry treatment composition comprising polymeric lubricants
CN2009801087616A CN101970632B (en) 2008-03-14 2009-01-22 Laundry treatment composition comprising polymeric lubricants
ZA2010/05759A ZA201005759B (en) 2008-03-14 2010-08-12 Laundry treatment composition comprising polymeric lubricants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08152740.0 2008-03-14
EP08152740 2008-03-14

Publications (1)

Publication Number Publication Date
WO2009112298A1 true WO2009112298A1 (en) 2009-09-17

Family

ID=39666179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/050700 WO2009112298A1 (en) 2008-03-14 2009-01-22 Laundry treatment composition comprising polymeric lubricants

Country Status (6)

Country Link
EP (1) EP2252680B1 (en)
CN (1) CN101970632B (en)
BR (1) BRPI0909346A2 (en)
ES (1) ES2390112T3 (en)
WO (1) WO2009112298A1 (en)
ZA (1) ZA201005759B (en)

Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011134809A1 (en) 2010-04-26 2011-11-03 Novozymes A/S Enzyme granules
WO2012175708A2 (en) 2011-06-24 2012-12-27 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2012175401A2 (en) 2011-06-20 2012-12-27 Novozymes A/S Particulate composition
WO2013001087A2 (en) 2011-06-30 2013-01-03 Novozymes A/S Method for screening alpha-amylases
WO2013007594A1 (en) 2011-07-12 2013-01-17 Novozymes A/S Storage-stable enzyme granules
WO2013024021A1 (en) 2011-08-15 2013-02-21 Novozymes A/S Polypeptides having cellulase activity and polynucleotides encoding same
WO2013041689A1 (en) 2011-09-22 2013-03-28 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2013076269A1 (en) 2011-11-25 2013-05-30 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2013092635A1 (en) 2011-12-20 2013-06-27 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2013110766A1 (en) 2012-01-26 2013-08-01 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
WO2013120948A1 (en) 2012-02-17 2013-08-22 Novozymes A/S Subtilisin variants and polynucleotides encoding same
WO2013131964A1 (en) 2012-03-07 2013-09-12 Novozymes A/S Detergent composition and substitution of optical brighteners in detergent compositions
WO2013167581A1 (en) 2012-05-07 2013-11-14 Novozymes A/S Polypeptides having xanthan degrading activity and polynucleotides encoding same
WO2013189972A2 (en) 2012-06-20 2013-12-27 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
WO2014096259A1 (en) 2012-12-21 2014-06-26 Novozymes A/S Polypeptides having protease activiy and polynucleotides encoding same
WO2014183921A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
WO2014207224A1 (en) 2013-06-27 2014-12-31 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2014207227A1 (en) 2013-06-27 2014-12-31 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2015001017A2 (en) 2013-07-04 2015-01-08 Novozymes A/S Polypeptides having anti-redeposition effect and polynucleotides encoding same
EP2832853A1 (en) 2013-07-29 2015-02-04 Henkel AG&Co. KGAA Detergent composition comprising protease variants
WO2015049370A1 (en) 2013-10-03 2015-04-09 Novozymes A/S Detergent composition and use of detergent composition
WO2015134729A1 (en) 2014-03-05 2015-09-11 Novozymes A/S Compositions and methods for improving properties of non-cellulosic textile materials with xyloglucan endotransglycosylase
WO2015134737A1 (en) 2014-03-05 2015-09-11 Novozymes A/S Compositions and methods for improving properties of cellulosic textile materials with xyloglucan endotransglycosylase
WO2015150457A1 (en) 2014-04-01 2015-10-08 Novozymes A/S Polypeptides having alpha amylase activity
WO2015189371A1 (en) 2014-06-12 2015-12-17 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2016079305A1 (en) 2014-11-20 2016-05-26 Novozymes A/S Alicyclobacillus variants and polynucleotides encoding same
EP3106508A1 (en) 2015-06-18 2016-12-21 Henkel AG & Co. KGaA Detergent composition comprising subtilase variants
WO2017064253A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2017064269A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Polypeptide variants
WO2017207762A1 (en) 2016-06-03 2017-12-07 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2018011276A1 (en) 2016-07-13 2018-01-18 The Procter & Gamble Company Bacillus cibi dnase variants and uses thereof
EP3309249A1 (en) 2013-07-29 2018-04-18 Novozymes A/S Protease variants and polynucleotides encoding same
EP3321360A2 (en) 2013-01-03 2018-05-16 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
EP3453757A1 (en) 2013-12-20 2019-03-13 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2019081721A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants
WO2019084349A1 (en) 2017-10-27 2019-05-02 The Procter & Gamble Company Detergent compositions comprising polypeptide variants
WO2019201793A1 (en) 2018-04-17 2019-10-24 Novozymes A/S Polypeptides comprising carbohydrate binding activity in detergent compositions and their use in reducing wrinkles in textile or fabric.
EP3608403A2 (en) 2014-12-15 2020-02-12 Henkel AG & Co. KGaA Detergent composition comprising subtilase variants
EP3611260A1 (en) 2013-07-29 2020-02-19 Novozymes A/S Protease variants and polynucleotides encoding same
EP3690037A1 (en) 2014-12-04 2020-08-05 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2020188095A1 (en) 2019-03-21 2020-09-24 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2020207944A1 (en) 2019-04-10 2020-10-15 Novozymes A/S Polypeptide variants
EP3739029A1 (en) 2014-07-04 2020-11-18 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3786269A1 (en) 2013-06-06 2021-03-03 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2021037895A1 (en) 2019-08-27 2021-03-04 Novozymes A/S Detergent composition
WO2021053127A1 (en) 2019-09-19 2021-03-25 Novozymes A/S Detergent composition
WO2021064068A1 (en) 2019-10-03 2021-04-08 Novozymes A/S Polypeptides comprising at least two carbohydrate binding domains
EP3872175A1 (en) 2015-06-18 2021-09-01 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3878960A1 (en) 2014-07-04 2021-09-15 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3892708A1 (en) 2020-04-06 2021-10-13 Henkel AG & Co. KGaA Cleaning compositions comprising dispersin variants
WO2022074037A2 (en) 2020-10-07 2022-04-14 Novozymes A/S Alpha-amylase variants
WO2022171780A2 (en) 2021-02-12 2022-08-18 Novozymes A/S Alpha-amylase variants
WO2022268885A1 (en) 2021-06-23 2022-12-29 Novozymes A/S Alpha-amylase polypeptides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900002A1 (en) * 1969-01-02 1970-07-30 Henkel & Cie Gmbh Washing powder
EP0071422A1 (en) * 1981-07-27 1983-02-09 Milliken Research Corporation Powdered cleaning compositions
WO2003074644A1 (en) * 2002-02-28 2003-09-12 The Procter & Gamble Company Detergent compositions including dispersible polyolefin wax and method for using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900002A1 (en) * 1969-01-02 1970-07-30 Henkel & Cie Gmbh Washing powder
EP0071422A1 (en) * 1981-07-27 1983-02-09 Milliken Research Corporation Powdered cleaning compositions
WO2003074644A1 (en) * 2002-02-28 2003-09-12 The Procter & Gamble Company Detergent compositions including dispersible polyolefin wax and method for using same

Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011134809A1 (en) 2010-04-26 2011-11-03 Novozymes A/S Enzyme granules
EP2840134A1 (en) 2010-04-26 2015-02-25 Novozymes A/S Enzyme granules
WO2012175401A2 (en) 2011-06-20 2012-12-27 Novozymes A/S Particulate composition
WO2012175708A2 (en) 2011-06-24 2012-12-27 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2013001087A2 (en) 2011-06-30 2013-01-03 Novozymes A/S Method for screening alpha-amylases
EP3543333A2 (en) 2011-06-30 2019-09-25 Novozymes A/S Method for screening alpha-amylases
EP4026901A2 (en) 2011-06-30 2022-07-13 Novozymes A/S Method for screening alpha-amylases
WO2013007594A1 (en) 2011-07-12 2013-01-17 Novozymes A/S Storage-stable enzyme granules
WO2013024021A1 (en) 2011-08-15 2013-02-21 Novozymes A/S Polypeptides having cellulase activity and polynucleotides encoding same
WO2013041689A1 (en) 2011-09-22 2013-03-28 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2013076269A1 (en) 2011-11-25 2013-05-30 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2013092635A1 (en) 2011-12-20 2013-06-27 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2013110766A1 (en) 2012-01-26 2013-08-01 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
WO2013120948A1 (en) 2012-02-17 2013-08-22 Novozymes A/S Subtilisin variants and polynucleotides encoding same
WO2013131964A1 (en) 2012-03-07 2013-09-12 Novozymes A/S Detergent composition and substitution of optical brighteners in detergent compositions
WO2013167581A1 (en) 2012-05-07 2013-11-14 Novozymes A/S Polypeptides having xanthan degrading activity and polynucleotides encoding same
WO2013189972A2 (en) 2012-06-20 2013-12-27 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
WO2014096259A1 (en) 2012-12-21 2014-06-26 Novozymes A/S Polypeptides having protease activiy and polynucleotides encoding same
EP3321360A2 (en) 2013-01-03 2018-05-16 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2014183921A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
EP3786269A1 (en) 2013-06-06 2021-03-03 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2014207227A1 (en) 2013-06-27 2014-12-31 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2014207224A1 (en) 2013-06-27 2014-12-31 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2015001017A2 (en) 2013-07-04 2015-01-08 Novozymes A/S Polypeptides having anti-redeposition effect and polynucleotides encoding same
EP2832853A1 (en) 2013-07-29 2015-02-04 Henkel AG&Co. KGAA Detergent composition comprising protease variants
EP3613853A1 (en) 2013-07-29 2020-02-26 Novozymes A/S Protease variants and polynucleotides encoding same
EP3611260A1 (en) 2013-07-29 2020-02-19 Novozymes A/S Protease variants and polynucleotides encoding same
EP3339436A1 (en) 2013-07-29 2018-06-27 Henkel AG & Co. KGaA Detergent composition comprising protease variants
EP3309249A1 (en) 2013-07-29 2018-04-18 Novozymes A/S Protease variants and polynucleotides encoding same
WO2015049370A1 (en) 2013-10-03 2015-04-09 Novozymes A/S Detergent composition and use of detergent composition
EP3453757A1 (en) 2013-12-20 2019-03-13 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2015134729A1 (en) 2014-03-05 2015-09-11 Novozymes A/S Compositions and methods for improving properties of non-cellulosic textile materials with xyloglucan endotransglycosylase
WO2015134737A1 (en) 2014-03-05 2015-09-11 Novozymes A/S Compositions and methods for improving properties of cellulosic textile materials with xyloglucan endotransglycosylase
WO2015150457A1 (en) 2014-04-01 2015-10-08 Novozymes A/S Polypeptides having alpha amylase activity
WO2015189371A1 (en) 2014-06-12 2015-12-17 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
EP3878960A1 (en) 2014-07-04 2021-09-15 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3739029A1 (en) 2014-07-04 2020-11-18 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2016079305A1 (en) 2014-11-20 2016-05-26 Novozymes A/S Alicyclobacillus variants and polynucleotides encoding same
EP3690037A1 (en) 2014-12-04 2020-08-05 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3608403A2 (en) 2014-12-15 2020-02-12 Henkel AG & Co. KGaA Detergent composition comprising subtilase variants
US10760036B2 (en) 2014-12-15 2020-09-01 Henkel Ag & Co. Kgaa Detergent composition comprising subtilase variants
EP4071244A1 (en) 2015-06-18 2022-10-12 Novozymes A/S Subtilase variants and polynucleotides encoding same
EP3106508A1 (en) 2015-06-18 2016-12-21 Henkel AG & Co. KGaA Detergent composition comprising subtilase variants
EP3872175A1 (en) 2015-06-18 2021-09-01 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2017064253A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
WO2017064269A1 (en) 2015-10-14 2017-04-20 Novozymes A/S Polypeptide variants
EP4324919A2 (en) 2015-10-14 2024-02-21 Novozymes A/S Polypeptide variants
WO2017207762A1 (en) 2016-06-03 2017-12-07 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2018011276A1 (en) 2016-07-13 2018-01-18 The Procter & Gamble Company Bacillus cibi dnase variants and uses thereof
WO2018011277A1 (en) 2016-07-13 2018-01-18 Novozymes A/S Bacillus cibi dnase variants
EP3950941A2 (en) 2016-07-13 2022-02-09 Novozymes A/S Dnase polypeptide variants
WO2019081724A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants
WO2019084349A1 (en) 2017-10-27 2019-05-02 The Procter & Gamble Company Detergent compositions comprising polypeptide variants
WO2019081721A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants
WO2019201793A1 (en) 2018-04-17 2019-10-24 Novozymes A/S Polypeptides comprising carbohydrate binding activity in detergent compositions and their use in reducing wrinkles in textile or fabric.
WO2020188095A1 (en) 2019-03-21 2020-09-24 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2020207944A1 (en) 2019-04-10 2020-10-15 Novozymes A/S Polypeptide variants
WO2021037895A1 (en) 2019-08-27 2021-03-04 Novozymes A/S Detergent composition
WO2021053127A1 (en) 2019-09-19 2021-03-25 Novozymes A/S Detergent composition
WO2021064068A1 (en) 2019-10-03 2021-04-08 Novozymes A/S Polypeptides comprising at least two carbohydrate binding domains
EP3892708A1 (en) 2020-04-06 2021-10-13 Henkel AG & Co. KGaA Cleaning compositions comprising dispersin variants
WO2022074037A2 (en) 2020-10-07 2022-04-14 Novozymes A/S Alpha-amylase variants
WO2022171780A2 (en) 2021-02-12 2022-08-18 Novozymes A/S Alpha-amylase variants
WO2022268885A1 (en) 2021-06-23 2022-12-29 Novozymes A/S Alpha-amylase polypeptides

Also Published As

Publication number Publication date
EP2252680A1 (en) 2010-11-24
ZA201005759B (en) 2011-10-26
CN101970632B (en) 2012-11-07
CN101970632A (en) 2011-02-09
BRPI0909346A2 (en) 2016-07-05
EP2252680B1 (en) 2012-06-20
ES2390112T3 (en) 2012-11-06

Similar Documents

Publication Publication Date Title
EP2252680B1 (en) Laundry treatment composition comprising polymeric lubricants
EP2252678B1 (en) Laundry treatment compositions
EP2288686B1 (en) Shading composition
EP2297288B1 (en) Laundry compositions
EP2354214B2 (en) Surfactant ratio in dye formulations
WO2010102861A1 (en) Dye-polymers formulations
WO2013139702A1 (en) Laundry detergent particles
EP2103677A1 (en) Laundry treatment compositions
EP2252681B2 (en) Laundry treatment compositions
EP2360232A1 (en) Surfactant ratio in laundry detergents comprising a dye
WO2012172038A1 (en) Incorporation of dye into granular laundry composition
EP2521764B1 (en) Detergent formulation containing spray dried granule
EP2427540A1 (en) Shading composition
EP2331670B1 (en) Cationic isothiazolium dyes
EP2519624A1 (en) Shading composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980108761.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09719383

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2009719383

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1900/MUMNP/2010

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: PI0909346

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20100914