WO2009112296A1 - Compositions de traitement du linge - Google Patents
Compositions de traitement du linge Download PDFInfo
- Publication number
- WO2009112296A1 WO2009112296A1 PCT/EP2009/050698 EP2009050698W WO2009112296A1 WO 2009112296 A1 WO2009112296 A1 WO 2009112296A1 EP 2009050698 W EP2009050698 W EP 2009050698W WO 2009112296 A1 WO2009112296 A1 WO 2009112296A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laundry treatment
- siθ2
- spherical
- treatment composition
- range
- 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.)
- Ceased
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
Definitions
- the present invention relates to wash added, laundry detergent compositions and methods for using the same during the wash cycle of a consumer laundry process.
- WO 2007/111887 discloses liquid compositions comprising hueing dye and a pearlescent agent.
- the pearlescent agent is added to counteract the darkening effect of the hueing dye on the appearance of the liquid composition.
- the pearlescent agent may be organic or inorganic in nature, with glass or metal oxide coated glass being disclosed.
- Si ⁇ 2 particles provide improved colour care by reducing damage caused by fabric laundering.
- the present invention provides a granular laundry treatment composition containing less than 1 wt . % of phosphate comprising:
- the spherical Si ⁇ 2 particle is chosen from sand, therein having a size in the range of 1 to 2000 microns, and/or glass, therein having a size in the range of from 100 to 2000 microns.
- a second aspect of the invention provides a domestic method of treating a textile, the method comprising the steps of:
- a third aspect of the invention provides the use of spherical Si ⁇ 2 particles to reduce damage to clothes being laundered during a domestic main wash process.
- the spherical Si ⁇ 2 particle is chosen from sand, therein having a size in the range of 1 to 2000 microns, and/or glass, therein having a size in the range of from 100 to 2000 microns.
- the amount of components in the granular laundry treatment composition quoted herein are wt . % of total composition unless otherwise stated.
- the spherical Si ⁇ 2 particles should have a roundness (ratio of axes) of >80%, preferably >94%.
- the roundness (ratio of axes) is a measurement of the length/width relationship with values in the range 0 - 1.
- the length is the shortest axis and the width is the longest axis.
- a perfect circle has a roundness value of 1.0 and a thin rectangle values approaching 0.
- images of the particles should be taken, preferably with a suitable microscope, for example a PharmaVision 830 available from MalvernTM.
- the spherical Si ⁇ 2 particle is preferably chosen from sand, therein having a size in the range of 1 to 2000 microns, and/or glass, therein having a size in the range of from 100 to 2000 microns.
- the size of the spherical Si ⁇ 2 particle is 100 to 2000 microns, more preferably 100 to 1000 microns, even more preferably 100 to 500 microns, for example 100 to 200 microns .
- the size of the spherical Si ⁇ 2 particle is measured using graded sieves and it is that which is retained or passes through such sieves.
- the spherical Si ⁇ 2 particle comprises Si ⁇ 2 at a level of from 50 to 100 wt. %, preferably from 55 to 100 wt.%, more preferably from 65 to 100 wt.%.
- the Si ⁇ 2 particles may contain other components, examples of such being Na2 ⁇ 0, CaO and MgO. If present at all, the other components are preferably present at 45 wt.% or less, more preferably 35 wt.% or less based on wt.% of the Si ⁇ 2 particle .
- the composition comprises between 2 to 70 wt.% of a surfactant, most preferably 10 to 30 wt.%.
- a surfactant most preferably 10 to 30 wt.%.
- 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.
- 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.
- 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 Ci 5 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 Ci 5 alkyl benzene sulphonates and sodium C12 to Cis alkyl sulphates.
- 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) .
- surfactant system that is a mixture of an alkali metal salt of a C ⁇ ⁇ to Cis primary alcohol sulphate together with a C12 to Ci 5 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.
- 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.
- an insoluble inorganic builder e.g., zeolite
- the size is in the range 0.1 to 10 microns (as measured by The Mastersizer 2000 particle size analyzer using laser diffraction ex MalvernTM) .
- calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra- acetic acid.
- precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
- Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-O, 384, 070.
- zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-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.
- a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below.
- Many builders are also bleach- stabilising agents by virtue of their ability to complex metal ions.
- Zeolite and carbonate are preferred builders.
- 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 M 2 O . Al 2 O 3 . 0 . 8 - 6 S iO 2
- M is a monovalent cation, preferably sodium.
- M a monovalent cation, preferably sodium.
- These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g.
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
- the ratio of surfactants to aluminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
- phosphate builders may be used.
- ⁇ phosphate' embraces diphosphate, triphosphate, and phosphonate species.
- the composition comprises less than 1 wt . % of such phosphate builders.
- the laundry detergent formulation is a non-phosphate built laundry detergent formulation.
- builder examples include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) .
- silicates such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst) .
- 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) .
- a direct violet or direct blue dyes is present.
- 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 :
- 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
- 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.
- the granular laundry treatment composition preferably comprises one or more enzymes which provide cleaning performance and/or fabric care benefits.
- 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.
- 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.
- the composition preferably comprises a fluorescent agent (optical brightener) .
- fluorescent agents are well known and many such fluorescent agents are available commercially.
- 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 .
- the composition comprises a perfume.
- the perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt . % .
- CTFA Cosmetic, Toiletry and Fragrance Association
- compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
- top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2) : 80 [1955]) .
- Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol .
- Perfume and top note may be used to cue the fabric care benefit of the invention.
- the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
- a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
- the composition may comprise one or more polymers.
- polymers include 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 .
- 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 ⁇ R (powder control) for Vat Blue was 6.06 and for Reactive Orange was 5.36.
- the average ⁇ R for the blue and orange cloths is given to 1 decimal place.
- Sand was obtained from Schlingmeier Quartz sand and had a SiO 2 content of 98.9%
- Silica-alumino ceramic microsphere particles were obtained from 3M.
- the Silica-alumino ceramic microsphere examples are comparative, and show the advantage of the Si ⁇ 2 particles in comparison to other spherical inorganic particles.
- the Si ⁇ 2 particles maintain the cloth closer to the new, as indicated by smaller ⁇ R430 values.
- NI (7EO) refers to R- (OCH 2 CH 2 ) n 0H, where R is an alkyl chain of C12 to C15, and n is 7.
- the formulations are prepared by adding direct violet 9, and the Sulfonated Zn Pthalocyanine photobleach into the slurry which is then spray dried.
- the dyes and photobleach may be added via post-dosed MgSO 4 granules.
- the solvent violet 13 was dissolved in non-ionic surfactant (7EO) to give a 0.5 wt% solution and granulated onto bentonite clay, to give a granule containing 0.2wt% dye. This was post-dosed to the formulation.
- the glass bead (Sigmund Lindner) was added in two ways, by addition to the slurry and by post-dosing. It was noted the bead aided flow of the powder.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Silicon Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0908060A BRPI0908060A2 (pt) | 2008-03-14 | 2009-01-22 | composição granular de tratamento de tecidos, método doméstico para tratar tecidos, e, uso de partículas de si02 esféricas |
| ES09718739.7T ES2379979T5 (es) | 2008-03-14 | 2009-01-22 | Composición de tratamiento de colada |
| CN2009801087457A CN101970631B (zh) | 2008-03-14 | 2009-01-22 | 洗衣处理组合物 |
| EP09718739.7A EP2252678B2 (fr) | 2008-03-14 | 2009-01-22 | Compositions de traitement du linge |
| AT09718739T ATE539140T1 (de) | 2008-03-14 | 2009-01-22 | Wäschebehandlungsmittel |
| ZA2010/05763A ZA201005763B (en) | 2008-03-14 | 2010-08-12 | Laundry treatment compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08152742.6 | 2008-03-14 | ||
| EP08152742 | 2008-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009112296A1 true WO2009112296A1 (fr) | 2009-09-17 |
Family
ID=39708831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2009/050698 Ceased WO2009112296A1 (fr) | 2008-03-14 | 2009-01-22 | Compositions de traitement du linge |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2252678B2 (fr) |
| CN (1) | CN101970631B (fr) |
| AT (1) | ATE539140T1 (fr) |
| BR (1) | BRPI0908060A2 (fr) |
| ES (1) | ES2379979T5 (fr) |
| WO (1) | WO2009112296A1 (fr) |
| ZA (1) | ZA201005763B (fr) |
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| WO2020207944A1 (fr) | 2019-04-10 | 2020-10-15 | Novozymes A/S | Variants polypeptidiques |
| EP3739029A1 (fr) | 2014-07-04 | 2020-11-18 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
| EP3786269A1 (fr) | 2013-06-06 | 2021-03-03 | Novozymes A/S | Variants d'alpha-amylase et polynucléotides les codant |
| WO2021037895A1 (fr) | 2019-08-27 | 2021-03-04 | Novozymes A/S | Composition détergente |
| WO2021053127A1 (fr) | 2019-09-19 | 2021-03-25 | Novozymes A/S | Composition détergente |
| WO2021064068A1 (fr) | 2019-10-03 | 2021-04-08 | Novozymes A/S | Polypeptides comprenant au moins deux domaines de liaison aux hydrates de carbone |
| EP3872175A1 (fr) | 2015-06-18 | 2021-09-01 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
| EP3878960A1 (fr) | 2014-07-04 | 2021-09-15 | Novozymes A/S | Variants de subtilase et polynucléotides codant pour ceux-ci |
| EP3892708A1 (fr) | 2020-04-06 | 2021-10-13 | Henkel AG & Co. KGaA | Compositions de nettoyage comprenant des variantes de dispersine |
| WO2022074037A2 (fr) | 2020-10-07 | 2022-04-14 | Novozymes A/S | Variants d'alpha-amylase |
| WO2022171780A2 (fr) | 2021-02-12 | 2022-08-18 | Novozymes A/S | Variants d'alpha-amylase |
| WO2022268885A1 (fr) | 2021-06-23 | 2022-12-29 | Novozymes A/S | Polypeptides d'alpha-amylase |
| WO2024131880A2 (fr) | 2022-12-23 | 2024-06-27 | Novozymes A/S | Composition détergente comprenant une catalase et une amylase |
| US12330186B2 (en) * | 2017-11-02 | 2025-06-17 | Preferred Technology, Llc | Continuous mixers and methods of using the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2674475A1 (fr) * | 2012-06-11 | 2013-12-18 | The Procter & Gamble Company | Composition détergente |
| US9828569B2 (en) | 2013-06-13 | 2017-11-28 | The Procter & Gamble Company | Granular laundry detergent |
| CN108251236A (zh) * | 2018-02-26 | 2018-07-06 | 合肥远科服装设计有限公司 | 一种高性能的环保型洗衣液及其制备方法 |
| CN109234031A (zh) * | 2018-09-25 | 2019-01-18 | 安顺市永烁科技有限公司 | 一种洗涤布草用洗衣粉 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051046A (en) * | 1973-02-16 | 1977-09-27 | The Procter & Gamble Company | Detergent compositions containing insoluble particulate materials having fabric conditioning properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0820762A1 (fr) † | 1996-07-15 | 1998-01-28 | Unilever Plc | Compositions de parfums |
| GB9825558D0 (en) * | 1998-11-20 | 1999-01-13 | Unilever Plc | Granular detergent components and particulate detergent compositions containing them |
-
2009
- 2009-01-22 WO PCT/EP2009/050698 patent/WO2009112296A1/fr not_active Ceased
- 2009-01-22 AT AT09718739T patent/ATE539140T1/de active
- 2009-01-22 BR BRPI0908060A patent/BRPI0908060A2/pt not_active IP Right Cessation
- 2009-01-22 EP EP09718739.7A patent/EP2252678B2/fr not_active Not-in-force
- 2009-01-22 ES ES09718739.7T patent/ES2379979T5/es active Active
- 2009-01-22 CN CN2009801087457A patent/CN101970631B/zh not_active Expired - Fee Related
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- 2010-08-12 ZA ZA2010/05763A patent/ZA201005763B/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4051046A (en) * | 1973-02-16 | 1977-09-27 | The Procter & Gamble Company | Detergent compositions containing insoluble particulate materials having fabric conditioning properties |
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Also Published As
| Publication number | Publication date |
|---|---|
| ZA201005763B (en) | 2011-10-26 |
| EP2252678B2 (fr) | 2016-10-26 |
| ES2379979T3 (es) | 2012-05-07 |
| EP2252678A1 (fr) | 2010-11-24 |
| EP2252678B1 (fr) | 2011-12-28 |
| ES2379979T5 (es) | 2017-02-17 |
| BRPI0908060A2 (pt) | 2019-09-24 |
| CN101970631B (zh) | 2012-10-10 |
| CN101970631A (zh) | 2011-02-09 |
| ATE539140T1 (de) | 2012-01-15 |
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