WO2001044561A1 - Procede et composition de blanchissage d'etoffes - Google Patents
Procede et composition de blanchissage d'etoffes Download PDFInfo
- Publication number
- WO2001044561A1 WO2001044561A1 PCT/EP2000/011563 EP0011563W WO0144561A1 WO 2001044561 A1 WO2001044561 A1 WO 2001044561A1 EP 0011563 W EP0011563 W EP 0011563W WO 0144561 A1 WO0144561 A1 WO 0144561A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- surfactant
- rinse
- salt
- clays
- 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
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- 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
Definitions
- the present invention relates to a process and a composition for the laundering of textile fabrics.
- the inventors have conjectured that the clay exerts its effect by remaining on the clothes after they have dried and acts as a sacrificial layer, to which dirt adheres and so is more easily removed during subsequent washing the next time. This avoids a build-up of particulate soil on the fabric.
- Pelletised compositions comprising, inter alia, smectite clay and magnesium sulphate for fibre softening use, are disclosed in JP-A-10 331066 and JP-A-10 331067.
- a fabric softening composition which may be used in the rinse cycle, containing a fabric softening bentonite clay and an isostearamide antistatic agent is disclosed in GB-A-2 170 236.
- Exemplified compositions contian surfactant.
- Other compositions containing clay, water soluble non-surfactant salt (electrolyte) and surfactant, are disclosed in GB-A-2207 144, GB-A-2 170236, GB-A-1 303 810, EP-A- 0 947 203, EP-A-0 146289, EP-A-0 139330 and EP-A-0026529.
- a first aspect of the present invention provides a process for the laundering of textile fabrics, which comprises:
- a second aspect of the present invention provides a composition for treating laundered textile fabrics in the rinse, which comprises: (a) from 2 to 98 wt% of a light coloured crystalline clay mineral; and (b) from 98 to 2 wt% of a water-soluble inorganic salt, the weight ratio of (a):(b) being from 49:1 to 1:49, preferably from 20:1 to 1:2, more preferably from 10:1 to 1 :2, and the composition being substantially free of non-soap surfactant.
- the present invention exerts its beneficial effect by incorporation of a light coloured crystalline clay material in the rinse liquor, also with a non-surfactant water-soluble salt.
- a non-surfactant water-soluble salt there may be more than one rinse but at least one rinse must conform with rinse step (ii) according to the present invention.
- the rinse liquor in step (ii) is substantially free of detergent.
- the rinse liquor in step (ii) preferably contains ⁇ 0.25g/l, more preferably ⁇ 0.1g/l, most preferably ⁇ 0.05g/l of synthetic non-soap surfactant and most preferably is completely devoid of such surfactant.
- the wash step (i) utilises an aqueous wash liquor comprising detergent surfactant, detergency builder and optionally, other ingredients. This will normally be formed from dissolving a detergent wash product containing these ingredients.
- composition of a suitable wash product typically comprises one or more deterging synthetic non-soap surfactants, chosen from anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof, as will be well known to those skilled in the art. Soap may also be included in the composition.
- synthetic non-soap surfactants chosen from anionic, nonionic, cationic and zwitterionic surfactants and mixtures thereof, as will be well known to those skilled in the art. Soap may also be included in the composition.
- surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
- the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and non-ionic compounds.
- compositions of the wash product may for example contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of C_-Ci5. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
- compositions of the wash product may contain other anionic surfactants in amounts additional to the percentages quoted above.
- Suitable anionic surfactants are well- known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly C 8 -C ⁇ 5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Sodium salts are generally preferred.
- compositions of the wash product may also contain non-ionic surfactant.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 2 o aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C ⁇ o-Cj 5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
- the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
- Cationic surfactants which can be used in main-wash compositions for fabrics.
- Cationic surfactants that may be used include quaternary ammonium salts of the general formula R ⁇ R 2 R 3 R 4 N + X " wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R, is a C 8 .C 2 2 alkyl group, preferably a C 8 -C ⁇ 0 or C 12 -C ⁇ 4 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
- surfactant surface-active compound
- amount present will depend on the intended use of the detergent composition.
- surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
- the total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2- 60%, preferably 15-40% most preferably 25-35%.
- Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
- compositions of the main wash product also contain one or more detergency builders.
- the total amount of detergency builder in the wash compositions will typically range from 5 to 80 wt%, preferably from 10 to 60 wt%.
- Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1
- compositions of the wash product preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
- Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
- the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O. AI 2 O 3 . 0.8-6 SiO 2
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
- the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
- the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384070A (Unilever).
- Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
- zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
- the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
- organic builders such as citrates, suitable used in amounts of from 5 to 30 wt%, preferably from 10 to 5 wt% are used.
- Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
- compositions according to the second aspect of the present invention are substantially free of synthetic non-soap surfactant, for example containing less than 10%, preferably less than 5%, more preferably less than 1%, especially less than 1% or substantially zero% by weight of the composition of such surfactant.
- Typical use concentrations are from 1 to 5, e.g. 2.5 grams/litre of water.
- compositions according to the present invention contain from 2 to 98 % by weight of a light coloured crystalline clay material, so as to be suitable for yielding preferably at least 0.02 g/l, more preferably at least 0.1 g/l of the clay in the rinse liquor, and preferably no more than 30g/l.
- crystalline clay mineral is selected from one or more clays selected from one or more clays selected from bi-layer clays, e.g. china clay and halloysite, dioctahedral clays such as kaolinite, trioctahedral clays such as antigorite and amesite, smectite and hormite clays such as bentonite (montmorillonite), beidelite, nontronite, hectorite, attapulgite, pimelite, mica, muscovite and vermiculite clays, as well as pyrophyllite/talc, willemseite and minnesotaite clays.
- bi-layer clays e.g. china clay and halloysite
- dioctahedral clays such as kaolinite
- trioctahedral clays such as antigorite and amesite
- smectite and hormite clays such as bentonite (montmor
- the crystalline clay mineral must be light coloured. Preferably, it should have a reflectance of at least 60, more preferably at least 70, especially at least 80 at a wavelength of 460 nm. Preferably also, the number average particle diameter of the clay mineral particles should not exceed 2 ⁇ m, especially not exceeding 1 ⁇ m. This particle size diameter is that obtained measured by use of a Malvern ZetasizerTM , using a dispersion of the clay mineral at 0.1 g/l in deionised water at 25°C, the clay being dispersed by vigorous hand agitation using a glass rod stirrer for 1 minute.
- Optional Water-soluble Salt is that obtained measured by use of a Malvern ZetasizerTM , using a dispersion of the clay mineral at 0.1 g/l in deionised water at 25°C, the clay being dispersed by vigorous hand agitation using a glass rod stirrer for 1 minute.
- the optional water-soluble salt is believed to be beneficial because it promotes dispersion and assists flocculation of the clay particles in the rinse liquor and enables them to be uniformly dispersed in so deposit more uniformly on the fabric.
- non-surfactant water-soluble salt Any non-surfactant water-soluble salt may be used.
- non-surfactant salt is used because many surfactants, e.g. anionic surfactants are in the form of water soluble alkali metal salts and cationic surfactants are usually in water-soluble salt form with a counter-anion.
- salts of the metal cations with inorganic or organic anions are appropriate.
- a mixture of salts may also be used, but it is preferable to use a material which is widely available at low cost.
- a soluble salt of a monovalent metal such as an alkali metal, for example sodium or potassium, e.g. as the chloride or sulphate.
- the salt comprises magnesium ions.
- Magnesium chloride and/or sulphate are typical.
- the amount of salt used will depend on the valency of the metal but in the broadest concept, it will be used at a molar concentration of from 0.001 M to 1M. In the case of the magnesium salt, the molar concentration will usually be from 0.001 M to 0.1M in the rinse liquor.
- the amount of the water-soluble inorganic salt will be from 2-98 % by weight of the composition and in particular, for a magnesium chloride and/or sulphate, from 5 to 70 % by weight.
- compositions of the present invention optionally may contain one or more additional benefit agents for subsequent dispersion and/or solution in the wash step (i) and/or in the rinse liquor of step (ii).
- additional benefit agents for subsequent dispersion and/or solution in the wash step (i) and/or in the rinse liquor of step (ii).
- These may, for example, be selected from fluorescers, perfumes, starches, enzymes such as lipases, soil-release polymers, photobleaches and blueing agents.
- the composition, and therefore the rinse liquor is preferably substantially free from organic surfactant.
- Detergency builders may also be included. Those which are water-soluble salts will form all or part of the water-soluble salt (b) if used in rinse step (ii).
- Any fluorescer present is preferably incorporated in an amount of from 0.01 to 1% by weight of the composition, although the upper limit of this range is more preferably, 0.75%, still more preferably 0.5%, most preferably 0.1% by weight of the composition.
- Typical perfume levels are from 0.1% to 1%, e.g. from 0.2% to 0.5% by weight of the composition.
- compositions of the present invention may be provided in any suitable form to allow convenient dispersion/solution in the rinse liquor by the consumer.
- they may be provided as powders or granulated solids. They may also be provided in any of the forms of liquids, pastes, gels, bars or tablets.
- the compositions may be provided in a product form whereby they are provided alongside a main wash product, for example comprising a detergent surfactant, a detergency builder and optionally, other detergent ingredients.
- the main wash product and the rinse composition according to the present invention may be provided in respective secondary packaging inside a unitary primary package.
- the soiling method imitates the environmental soiling conditions experienced in urban smogs. This was achieved by placing samples of fabric, within a purpose built frame and then exposing the frame to conditions within an exhaust chamber of the Mersey Tunnel (George's Dock Building). The samples were subjected to an exposure period of one week.
- Clay rinse treatment 2. Expose to Mersey Tunnel for one week.
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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)
Abstract
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU25077/01A AU2507701A (en) | 1999-12-16 | 2000-11-17 | Process and composition for laundering of textile fabrics |
| BR0016207-8A BR0016207A (pt) | 1999-12-16 | 2000-11-17 | Processo para a lavagem de tecidos têxteis, composição para tratar tecidos têxteis lavados no enxágue, e, produto detergente para lavagem de roupas. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9929838.2A GB9929838D0 (en) | 1999-12-16 | 1999-12-16 | Process and composition for laundering of textile fabrics |
| GB9929838.2 | 1999-12-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001044561A1 true WO2001044561A1 (fr) | 2001-06-21 |
Family
ID=10866499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2000/011563 Ceased WO2001044561A1 (fr) | 1999-12-16 | 2000-11-17 | Procede et composition de blanchissage d'etoffes |
Country Status (7)
| Country | Link |
|---|---|
| CN (1) | CN1250695C (fr) |
| AU (1) | AU2507701A (fr) |
| BR (1) | BR0016207A (fr) |
| GB (1) | GB9929838D0 (fr) |
| TR (1) | TR200201563T2 (fr) |
| WO (1) | WO2001044561A1 (fr) |
| ZA (1) | ZA200203696B (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6565924B2 (en) | 2000-08-01 | 2003-05-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Textile treatment process and product |
| US6645569B2 (en) | 2001-01-30 | 2003-11-11 | The Procter & Gamble Company | Method of applying nanoparticles |
| WO2009148801A1 (fr) * | 2008-06-06 | 2009-12-10 | The Procter & Gamble Company | Procédé de lavage de linge à la main |
| WO2009148800A1 (fr) * | 2008-06-06 | 2009-12-10 | The Procter & Gamble Company | Système de lavage de linge à la main |
| EP4036200A1 (fr) * | 2021-02-02 | 2022-08-03 | Calik Denim Tekstil San. Ve Tic. A.S. | Dispersion, utilisations, procédés, appareils d'une ligne de lavage et ligne de fabrication de bande de tissu pour le lavage d'une bande de tissu avec de l'argile bentonite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4569773A (en) * | 1982-12-13 | 1986-02-11 | Colgate Palmolive Co. | Particulate fabric softening detergent composition |
| US4680916A (en) * | 1985-01-07 | 1987-07-21 | Ginn Martin E | Staged detergent/fabric treating preparation for use in washing machines |
| US5234620A (en) * | 1989-06-02 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent composition containing modified dioctanedral fabric softening clay having from 100-10,000 micrograms of non-exchangeable lithium per gram of clay |
-
1999
- 1999-12-16 GB GBGB9929838.2A patent/GB9929838D0/en not_active Ceased
-
2000
- 2000-11-17 CN CN00817313.3A patent/CN1250695C/zh not_active Expired - Fee Related
- 2000-11-17 TR TR2002/01563T patent/TR200201563T2/xx unknown
- 2000-11-17 AU AU25077/01A patent/AU2507701A/en not_active Abandoned
- 2000-11-17 BR BR0016207-8A patent/BR0016207A/pt not_active Application Discontinuation
- 2000-11-17 WO PCT/EP2000/011563 patent/WO2001044561A1/fr not_active Ceased
-
2002
- 2002-05-09 ZA ZA200203696A patent/ZA200203696B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4569773A (en) * | 1982-12-13 | 1986-02-11 | Colgate Palmolive Co. | Particulate fabric softening detergent composition |
| US4680916A (en) * | 1985-01-07 | 1987-07-21 | Ginn Martin E | Staged detergent/fabric treating preparation for use in washing machines |
| US5234620A (en) * | 1989-06-02 | 1993-08-10 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent composition containing modified dioctanedral fabric softening clay having from 100-10,000 micrograms of non-exchangeable lithium per gram of clay |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6565924B2 (en) | 2000-08-01 | 2003-05-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Textile treatment process and product |
| US6645569B2 (en) | 2001-01-30 | 2003-11-11 | The Procter & Gamble Company | Method of applying nanoparticles |
| US6863933B2 (en) | 2001-01-30 | 2005-03-08 | The Procter And Gamble Company | Method of hydrophilizing materials |
| US6872444B2 (en) | 2001-01-30 | 2005-03-29 | The Procter & Gamble Company | Enhancement of color on surfaces |
| US7112621B2 (en) | 2001-01-30 | 2006-09-26 | The Proctor & Gamble Company | Coating compositions for modifying surfaces |
| WO2009148801A1 (fr) * | 2008-06-06 | 2009-12-10 | The Procter & Gamble Company | Procédé de lavage de linge à la main |
| WO2009148800A1 (fr) * | 2008-06-06 | 2009-12-10 | The Procter & Gamble Company | Système de lavage de linge à la main |
| EP4036200A1 (fr) * | 2021-02-02 | 2022-08-03 | Calik Denim Tekstil San. Ve Tic. A.S. | Dispersion, utilisations, procédés, appareils d'une ligne de lavage et ligne de fabrication de bande de tissu pour le lavage d'une bande de tissu avec de l'argile bentonite |
| WO2022167392A1 (fr) * | 2021-02-02 | 2022-08-11 | Calik Denim Tekstil San. Ve Tic. A.S. | Dispersion, utilisations, procédés, appareils, chaîne de lavage et chaîne de fabrication de bande de tissu pour laver une bande textile avec de l'argile de bentonite |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0016207A (pt) | 2002-10-01 |
| GB9929838D0 (en) | 2000-02-09 |
| TR200201563T2 (tr) | 2002-10-21 |
| CN1250695C (zh) | 2006-04-12 |
| AU2507701A (en) | 2001-06-25 |
| CN1411521A (zh) | 2003-04-16 |
| ZA200203696B (en) | 2003-05-09 |
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