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EP2162522B1 - Compositions détergentes enzymatiques granulaires - Google Patents

Compositions détergentes enzymatiques granulaires Download PDF

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Publication number
EP2162522B1
EP2162522B1 EP08760075.5A EP08760075A EP2162522B1 EP 2162522 B1 EP2162522 B1 EP 2162522B1 EP 08760075 A EP08760075 A EP 08760075A EP 2162522 B1 EP2162522 B1 EP 2162522B1
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EP
European Patent Office
Prior art keywords
detergent composition
composition according
sodium
mes
weight
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Application number
EP08760075.5A
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German (de)
English (en)
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EP2162522A1 (fr
Inventor
Olaf C P Beers
Willem Oldenburg
Ronaldus T L Van Vliet
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
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Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP08760075.5A priority Critical patent/EP2162522B1/fr
Publication of EP2162522A1 publication Critical patent/EP2162522A1/fr
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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
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the present invention relates to granular detergent compositions, more in particular to granular detergent compositions comprising alkyl ester, in particular methyl ester fatty acid sulphonate surfactant and enzyme granules.
  • Laundry detergent compositions have for many years contained anionic sulphonate or sulphate surfactant, for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS), together with ethoxylated alcohol nonionic surfactants.
  • anionic sulphonate or sulphate surfactant for example, linear alkylbenzene sulphonate (LAS) or primary alkyl sulphate (PAS)
  • ethoxylated alcohol nonionic surfactants used in laundry detergent compositions include typically ethoxylated C 10 -C 16 alcohols having an average degree of ethoxylation of 3 to 9.
  • MES methyl ester fatty acid sulphonate
  • C16 MES Hexadecanoic acid, 2-sulfo-, 1-methylester, sodium salt (C17H33NaO5S)
  • Methyl ester sulphonate can be obtained by sulphonation of various renewable oleo-based methyl ester feedstocks derived from eg. coconut (C12-14), palm kernel (C8-18), palm stearin C16-18) or tallow (C16-18).
  • renewable origin MES is of special interest due to good biodegradability, detergency and calcium hardness tolerance.
  • EP-A-1 634 941 (Lion ) or WO-A-01/90284 (Huish ) disclose high bulk density granular detergents containing surfactants (including ⁇ -sulpho-fatty acid esters), (bi) carbonate, zeolite and a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
  • surfactants including ⁇ -sulpho-fatty acid esters
  • carbonate zeolite
  • zeolite a polymer containing of monoethylenic unsaturated mono- and di-carboxylic acid units.
  • US 4 194 986 discloses a detergent composition
  • a detergent composition comprising on the basis of 100 parts by weight of total composition, at least 60 parts of soap and no more than 10 parts of a mixture of surfactants comprising 10 to 30% of at least one non-ionic polyalkoxylated surfactant and 90 to 70% of an anionic surfactant selected essentially from ⁇ -sulfonated fatty acid derivatives, the remainder of the composition comprising at least one ingredient selected from alkaline detergent additives, bleaching agents, optical brighteners, fragrances, antiredeposition agents and enzymes.
  • the granular detergent composition according to the invention comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and enzyme granules, wherein said composition is substantially free of thiosulphate.
  • a granular detergent composition comprising 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant and 0.1 to 10% by weight enzyme granules, wherein said composition is substantially free of thiosulphate, and wherein said detergent composition comprises methyl sulphate.
  • a detergent tablet obtained by compressing the granular detergent composition according to the invention.
  • a process for laundering textile fabrics by machine or hand characterised in that it comprises the step of immersing the fabrics in a wash liquor comprising water in which a granular detergent composition or detergent tablet according to the invention is dissolved or dispersed.
  • the granular detergent composition of the invention comprises 1 to 30% by weight of an alkyl ester fatty acid sulphonate surfactant, preferably methyl ester fatty acid sulphonate surfactant, and enzyme granules.
  • an alkyl ester fatty acid sulphonate surfactant preferably methyl ester fatty acid sulphonate surfactant
  • enzyme granules Preferably, the amount of ⁇ -sulpho-fatty acid esters is 1 to 15% by weight, more preferably 3 to 8% by weight.
  • ⁇ -Sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, oil, coco butter, palm oil, white grease, cottonseed oil, corn oil, rape seed oil, soybean oil, yellow grease, mixtures thereof or fractions thereof.
  • Suitable fatty acids to make ⁇ -sulfofatty acid esters include, but are not limited to, caprylic (C 8 ), capric ((C 10 ), lauric (C 12 ), myristic (C 14 ), myristoleic (C 14 ), palmitic (C 16 ), palmitoleic (C 16 ), stearic (C 18 ), oleic (C 18 ), linoleic (C 18 ), linolenic (C 18 ), ricinoleic (C 18 ), arachidic (C 20 ), gadolic (C 20 ), behenic (C 22 ), and erucic (C 22 ) fatty acids.
  • ⁇ -Sulfofatty acid esters prepared from one or more of these sources are within the scope of the present invention.
  • Samples of alkyl ester fatty acid sulphonate surfactant prepared in dry powder form via above mentioned production processes typically contain about 75-85 % by weight of the desired surfactant.
  • the other components in a typical production sample there is one of specific relevance for the present invention, which is sodium methylsulphate, typically present at (but not restricted to) a level of about 1-10 % based on the weight of the MES as such.
  • the composition may also comprise one or more other surfactants.
  • the other surfactant is present in an amount of from 5 to 40 wt.%, preferably from 7 to 30 wt.%, based on the weight of the total composition.
  • alkylbenzene sulphonates examples include alkylbenzene sulphonates, branched or linear alkyl benzene sulphonates, primary and secondary alcohol sulphates, particularly C 8 -C 16 primary alcohol sulphates; alkyl ether sulphates, olefin sulphonates, including alpha olefin sulphonates, alkane sulphonates, alkyl xylene sulphonates, dialkyl sulphosuccinates, and alkyl carboxylates. These may be present as sodium, potassium, calcium or magnesium salts or mixtures of these. Sodium salts are generally preferred.
  • the other surfactant is preferably a sulphonate or sulphate anionic surfactant or a combination thereof. More preferably, the anionic surfactant is linear alkylbenzene sulphonate or primary alkyl sulphate. Most preferably the other surfactant is linear alkylbenzene sulphonate.
  • the linear alkyl benzene sulphonate may be present as sodium, potassium, or alkaline earth metal salts, or mixtures of these salts. Sodium salts are generally preferred.
  • the other surfactant may also comprise a nonionic surfactant, preferably an ethoxylated alcohol nonionic surfactant with an average degree of ethoxylation ranging from about 3 to 9, preferably from about 3 to 7.
  • the alcohol may be derived from natural or synthetic feedstock. Preferred alcohol feedstocks are coconut and palm kernel, predominantly C 12 -C 14 , and oxo C 12 -C 15 alcohols.
  • the nonionic surfactant is suitably present in an amount of from 1 to 20 wt %, preferably from 1 to 10, more preferably from 2 to 6 wt %, most preferably from 3 to 5 wt %, based on the weight of the total composition.
  • Additional surfactants or detergent active compounds may comprise other nonionics such as alkylpolyglucosides, polyhydroxyamides (glucamide), methyl ester ethoxylates and glycerol monoethers.
  • cationic, amphoteric surfactants and/or zwitterionic surfactants may be present.
  • Preferred cationic surfactants are quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X - , for example where R 1 is a C 12 -C 14 alkyl group, R 2 and R 3 are methyl groups, R 4 is a 2-hydroxyethyl group, and X - is a chloride ion. This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40 wt% aqueous solution.
  • Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide.
  • Preferred zwitterionic surfactants are betaines, and especially amidobetaines.
  • Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition.
  • the detergent compositions of the present invention comprise one or more other enzymes, which provide cleaning performance, fabric care and/or sanitation benefits.
  • Suitable enzymes for incorporation in detergent compositions preferably include protease, lipase, amylase, cellulase, mannanase and oxidase, peroxidise, oxidoreductase, beta-glucanase, pectinase and/or pectate lyase. Most preferably, the compositions contain a proteolytic enzyme or protease.
  • the composition may contain additional enzymes as found in WO-A-01/007681 page 15, line 25 to page19, line 29 as well as those found in WO-A-02/02726 page 16 line 21 to page 19 line 16 and those found in WO-A-02/02726 page 33 line 28 to page 39 line 34, the contents of which are herein incorporated by reference. It also may contain maltogenic ⁇ -amylases as described in WO-A-02/02726 page 5, line 14 to page 11 line 29. Commercially available maltogenic ⁇ -amylases are NovamylTM and MaltogenaseTM from Novozymes.
  • composition may also contain a lipase variant of the Humicola lanuginosa lipase with substitutions T231R + N233R, commercially available as LipexTM from Novozymes or another variant as described in WO-A-00/60063 .
  • composition may also contain other commercial enzymes not described in any of the previous specifications such as the new enzymes from Novozymes: MannawayTM, NatalaseTM, RenozymeTM, OvozymeTM, CelluCleanTM, PolarzymeTM, StainzymeTM, CoronaseTM, PectaawayTM, PectawashTM, Termamyl UltraTM. And the new enzymes from Genencor: FN-3, FN-4, Purafect PrimeTM, ProperaseTM.
  • detergency enzymes are employed in granular form in amounts of from about 0.1 to about 10.0 wt %, preferably from about 0.2 to about 3% by weight, more preferably from about 0.2 to about 1% by weight.
  • the detergent compositions are substantially free of thiosulphate. Since enzyme granules sometimes contain thiosulphate, it was found to be important to use thiosulphate free enzyme granules.
  • the amount of thiosulphate in the compositions can be determined using standard analytical techniques.
  • Thiosulphate in the context of this invention means any salt thereof, such as alkalimetal, especially sodium, but also ammonium, Monoethanolamine or Triethanolamine salts.
  • compositions of the invention may contain a detergency builder.
  • the builder is present in an amount of from 1 to less than 80 wt % based on the weight of the total composition. More preferably the amount of builder is from 1 to 60 wt %.
  • Builders are well-known to those skilled in the art. Many suitable builder compounds are available. Examples are zeolites, sodium tripolyphosphate, layered silicate, sodium carbonate, sodium bicarbonate, burkeite, sodium silicate and mixtures thereof.
  • compositions may optionally contain other active ingredients to enhance performance and properties.
  • compositions of the invention may contain from 0 to 85 wt % of an inorganic non-builder salt, such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite, preferably from 0 to 60 wt %, preferably from 0 to 40 wt %, based on the weight of the total composition.
  • an inorganic non-builder salt such as sodium sulphate, sodium sesquicarbonate, sodium chloride, calcium chloride, magnesium chloride and calcite
  • compositions of the invention may contain a polycarboxylate polymer.
  • polycarboxylate polymer include homopolymers and copolymers of acrylic acid, maleic acid and acrylic/maleic acids.
  • the publication 'Polymeric Dispersing Agents, Sokalan', a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic polymers which are useful.
  • the polycarboxylate polymer is selected from the group consisting of sodium polyacrylate, sodium acrylate maleate and mixtures thereof. Examples of suitable polymers include Sokalan CP5, ex BASF polyacrylate, namely maleic acid-acrylic acid copolymer, with a sodium salt.
  • the detergent compositions of the invention may comprise one or more optional ingredients selected from soap, peroxyacid and persalt bleaches, bleach activators, air bleach catalysts, sequestrants, cellulose ethers and esters, cellulosic polymers, other antiredeposition agents, sodium bicarbonate, other inorganic salts, fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, citric acid, soil release polymers, silicone, fabric conditioning compounds, coloured speckles such as blue speckles, and perfume. This list is not intended to be exhaustive.
  • compositions of the invention are granular detergent compositions, preferably in powder form, having a mean particle size between 200 and 800 micrometer. Alternatively, the compositions may be in tablet form.
  • the compositions can be formulated for use as hand wash or machine wash detergents.
  • the granular compositions of the invention may be prepared by any suitable process. Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a highspeed mixer/granulator, or other non-tower processes.
  • Tablets may be prepared by compacting powders, especially "concentrated" powders.
  • the choice of processing route may be in part dictated by the stability or heat-sensitivity of the surfactants involved, and the form in which they are available. In all cases, all ingredients may be added separately.
  • the malodour molecule generated during storage has been identified via GC/MS headspace analyses to be a dimethylsulfide (abbr. DMS), predominantly dimethyl-disulfide, dimethyl-trisulfide and dimethyl-tetrasulfide.
  • DMS dimethylsulfide
  • the severity of malodour due to dimethylsulfides can be best assessed olfactively using following intensity scale: intensity scale of DMTS-like malodour 0 no 1 moderate 2 strong 3 severe
  • MES in combination with thiosulphate-containing proteases in various products.
  • MES sodium methylsulphate in combination with thiosulphate-containing enzymes.
  • methylsulphate is one of the main by-products formed during MES production.
  • Malodour is due to an interaction of MES/MS and thiosulphate (which is present within enzyme-granules of Novozymes), since no malodour develops in the presence of thiosulphate-free enzymes from Genencor.

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  • 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)

Claims (16)

  1. Composition de détergent granulaire comprenant de 1 à 30 % en masse d'un tensio-actif de sulfonate d'acide gras d'ester alkylique et de 0,1 à 10 % en masse de granulés d'enzyme, dans laquelle ladite composition est pratiquement exempte de thiosulfate, et dans laquelle ladite composition de détergent comprend du sulfate de méthyle.
  2. Composition de détergent selon la revendication 1, dans laquelle le tensioactif de sulfonate d'acide gras d'ester alkylique est un tensioactif de sulfonate d'acide gras d'ester méthylique.
  3. Composition de détergent selon la revendication 1, contenant de 0,5 à 10 % de sulfate de méthyle, sur la base de la quantité de sulfonate d'acide gras d'ester méthylique.
  4. Composition de détergent selon l'une quelconque des revendications précédentes, dans laquelle l'enzyme est choisie dans le groupe constitué de protéase, lipase, amylase, cellulase, mananase et oxydoréductase.
  5. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant de plus un benzènesulfonate d'alkyle linéaire.
  6. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant un tensioactif non ionique d'alcool éthoxylé.
  7. Composition de détergent selon la revendication 6, dans laquelle le tensioactif non ionique d'alcool éthoxylé présente un degré moyen d'éthoxylation n de 3 à 7.
  8. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant un adjuvant dans une quantité de 1 à 60 %, de préférence de 1 à 40 % en masse.
  9. Composition de détergent selon la revendication 8, dans laquelle ledit adjuvant est choisi dans le groupe constitué de zéolite, tripolyphosphate de sodium, silicate lamellaire, carbonate de sodium, bicarbonate de sodium, burkéite, silicate de sodium et mélanges de ceux-ci.
  10. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant du sulfate de sodium dans une quantité de 2 à 50 %, de préférence de 10 à 40 % en masse.
  11. Composition de détergent selon la revendication 9, dans laquelle le silicate de sodium est présent dans une quantité de 1 à 20 % en masse.
  12. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant de plus un tensioactif cationique dans une quantité de 0,1 à 5 % en masse.
  13. Composition de détergent selon l'une quelconque des revendications précédentes, comprenant de plus un polymère de polycarboxylate choisi dans le groupe constitué de polyacrylate de sodium, acrylate maléate de sodium et mélanges de ceux-ci.
  14. Composition de détergent selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend de plus un ou plusieurs ingrédients facultatifs choisis parmi le savon, des blanchissants de peroxyacide et de persel, des activateurs de blanchiment, un catalyseur de blanchiment à l'air, des séquestrants, des éthers et esters de cellulose, des polymères cellulosiques, d'autres agents anti-redéposition, des azurants optiques, des photoblanchissants, de la polyvinylpyrrolidone, d'autres polymères inhibant le transfert de colorant, des agents de contrôle de mousse, des agents de promotion de mousse, des colorants, de l'acide citrique, des polymères libérant la saleté, des composés conditionnant les textiles, des billes colorées et du parfum.
  15. Tablette de détergent obtenue par compression de la composition de détergent granulaire selon l'une quelconque des revendications précédentes.
  16. Procédé de lessive de tissus textiles à la machine ou à la main, caractérisé en ce qu'il comprend l'étape d'immersion des tissus dans une liqueur de lavage comprenant de l'eau dans laquelle une composition de détergent granulaire ou une tablette de détergent selon l'une quelconque des revendications précédentes est dissoute ou dispersée.
EP08760075.5A 2007-06-22 2008-05-27 Compositions détergentes enzymatiques granulaires Active EP2162522B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08760075.5A EP2162522B1 (fr) 2007-06-22 2008-05-27 Compositions détergentes enzymatiques granulaires

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07110850 2007-06-22
PCT/EP2008/056477 WO2009000605A1 (fr) 2007-06-22 2008-05-27 Compositions détergentes enzymatiques granulaires
EP08760075.5A EP2162522B1 (fr) 2007-06-22 2008-05-27 Compositions détergentes enzymatiques granulaires

Publications (2)

Publication Number Publication Date
EP2162522A1 EP2162522A1 (fr) 2010-03-17
EP2162522B1 true EP2162522B1 (fr) 2018-07-04

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Country Status (7)

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EP (1) EP2162522B1 (fr)
CN (1) CN101688152B (fr)
AR (1) AR067053A1 (fr)
BR (1) BRPI0813386A2 (fr)
CL (1) CL2008001858A1 (fr)
TR (1) TR201810838T4 (fr)
WO (1) WO2009000605A1 (fr)

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US20170121695A1 (en) 2014-06-12 2017-05-04 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
US10626388B2 (en) 2014-07-04 2020-04-21 Novozymes A/S Subtilase variants and polynucleotides encoding same
CN106661566A (zh) 2014-07-04 2017-05-10 诺维信公司 枯草杆菌酶变体以及编码它们的多核苷酸
WO2016079305A1 (fr) 2014-11-20 2016-05-26 Novozymes A/S Variants de alicyclobacillus et polynucléotides codant pour ceux-ci
EP3690037A1 (fr) 2014-12-04 2020-08-05 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
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CN108291215A (zh) 2015-10-14 2018-07-17 诺维信公司 具有蛋白酶活性的多肽以及编码它们的多核苷酸
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HUE057832T2 (hu) 2017-10-27 2022-06-28 Procter & Gamble Polipeptid-variánsokat tartalmazó mosószerkészítmények
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MX2021011287A (es) 2019-03-21 2021-10-13 Novozymes As Variantes de alfa-amilasa y polinucleotidos que codifican las mismas.
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CN101688152A (zh) 2010-03-31
TR201810838T4 (tr) 2018-08-27
CN101688152B (zh) 2012-06-27
CL2008001858A1 (es) 2009-03-06
AR067053A1 (es) 2009-09-30
BRPI0813386A2 (pt) 2014-12-30
EP2162522A1 (fr) 2010-03-17
WO2009000605A1 (fr) 2008-12-31

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