EP2253741A3 - Process for the demulsifying cleaning of metallic surfaces - Google Patents
Process for the demulsifying cleaning of metallic surfaces Download PDFInfo
- Publication number
- EP2253741A3 EP2253741A3 EP10173888.8A EP10173888A EP2253741A3 EP 2253741 A3 EP2253741 A3 EP 2253741A3 EP 10173888 A EP10173888 A EP 10173888A EP 2253741 A3 EP2253741 A3 EP 2253741A3
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- organic compound
- demulsifying
- metallic surfaces
- anionic
- 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.)
- Granted
Links
- 238000004140 cleaning Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 title abstract 2
- 150000002894 organic compounds Chemical class 0.000 abstract 3
- 125000000129 anionic group Chemical group 0.000 abstract 2
- -1 anionic organic compound Chemical class 0.000 abstract 2
- 239000002245 particle Substances 0.000 abstract 2
- 239000000344 soap Substances 0.000 abstract 2
- 239000004519 grease Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—Organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur demulgierenden Reinigung von metallischen Oberflächen, die gegebenenfalls mit Öl(en), mit mindestens einer weiteren unpolaren organischen Verbindung, mit Fett(en), mit Seife(n), mit Partikelschmutz oder/und mit mindestens einer anionischen organischen Verbindung verschmutzt sind, mit einer wässerigen, alkalischen, Tensidhaltigen Badlösung, wobei das Bad beim Reinigen der metallischen Oberflächen mit Öl(en), mit mindestens einer weiteren unpolaren organischen Verbindung, mit Fett(en), mit Seife(n), mit Partikelschmutz oder/und mit mindestens einer anionischen organischen Verbindung verschmutzt wird, das dadurch gekennzeichnet ist, dass das Bad mindestens ein demulgierendes Tensid enthält oder/und dieses dem Bad zugesetzt wird, dass das Bad außerdem mindestens eine kationische organische Verbindung enthält oder/und diese dem Bad zugesetzt wird und dass das Bad auch bei zunehmender Verschmutzung insbesondere mit mindestens einer anionischen organischen Verbindung in einem demulgierenden Zustand gehalten wird.The invention relates to a process for the demulsifying purification of metallic surfaces, optionally with oil (s), with at least one other nonpolar organic compound, with fat (s), with soap (s), with particle dirt or / and with at least one anionic organic The bath when cleaning the metallic surfaces with oil (s), with at least one other non-polar organic compound, with grease (s), with soap (s), with particle dirt or / and contaminated with at least one anionic organic compound, characterized in that the bath contains at least one demulsifying surfactant and / or that is added to the bath, that the bath also contains at least one cationic organic compound and / or added to the bath and that the bath even with increasing pollution in particular with at least one anionic n organic compound is maintained in a demulsifying state.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006018216A DE102006018216B4 (en) | 2006-04-18 | 2006-04-18 | Process for the demulsifying cleaning of metallic surfaces |
EP07727340.7A EP2010696B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07727340.7A Division-Into EP2010696B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
EP07727340.7A Division EP2010696B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
EP07727340.7 Division | 2007-03-26 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2253741A2 EP2253741A2 (en) | 2010-11-24 |
EP2253741A3 true EP2253741A3 (en) | 2014-01-08 |
EP2253741B1 EP2253741B1 (en) | 2018-05-16 |
Family
ID=38266742
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07727340.7A Active EP2010696B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
EP10173888.8A Active EP2253741B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07727340.7A Active EP2010696B1 (en) | 2006-04-18 | 2007-03-26 | Process for the demulsifying cleaning of metallic surfaces |
Country Status (10)
Country | Link |
---|---|
US (4) | US20100068392A1 (en) |
EP (2) | EP2010696B1 (en) |
CN (2) | CN102787320B (en) |
BR (1) | BRPI0711624B1 (en) |
CA (1) | CA2650947C (en) |
DE (1) | DE102006018216B4 (en) |
ES (2) | ES2586573T3 (en) |
MX (1) | MX318016B (en) |
WO (1) | WO2007122056A1 (en) |
ZA (1) | ZA200809775B (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8557343B2 (en) | 2004-03-19 | 2013-10-15 | The Boeing Company | Activation method |
CN101103085B (en) | 2005-01-21 | 2012-12-26 | 联邦科学和工业研究组织 | Activation method using modifying agent |
DE102006018216B4 (en) | 2006-04-18 | 2008-09-25 | Chemetall Gmbh | Process for the demulsifying cleaning of metallic surfaces |
DE102007000501A1 (en) | 2007-10-15 | 2009-04-16 | Chemetall Gmbh | Cleaning composition for metallic surfaces |
WO2011084661A2 (en) | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Sulfonate-functional coatings and methods |
BR102012010852A2 (en) * | 2012-05-08 | 2015-04-14 | Oxiprana Ind Quimica Ltda | LEAD-FREE GALVANIZATION PROCESS FOR METAL MATERIALS |
CN103602995B (en) * | 2013-10-25 | 2016-04-06 | 青岛华仁技术孵化器有限公司 | Environmental protection type metal detergency agent |
DE102015206812A1 (en) | 2015-04-15 | 2016-10-20 | Henkel Ag & Co. Kgaa | Polymer-containing pre-rinse before a conversion treatment |
ES2763038T3 (en) | 2015-04-15 | 2020-05-26 | Henkel Ag & Co Kgaa | Thin corrosion protection coatings incorporating polyamidoamine polymers |
DE102015209910A1 (en) * | 2015-05-29 | 2016-12-01 | Henkel Ag & Co. Kgaa | Pre-rinse containing a quaternary amine for conditioning prior to a conversion treatment |
DE102015209909A1 (en) * | 2015-05-29 | 2016-12-01 | Henkel Ag & Co. Kgaa | Conditioning before a conversion treatment of metal surfaces |
CN111020604A (en) * | 2019-12-30 | 2020-04-17 | 奎克化学(中国)有限公司 | Water-based cleaning agent for ultrahigh-pressure spraying and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0054895A1 (en) * | 1980-12-23 | 1982-06-30 | Hoechst Aktiengesellschaft | Mixture of surfactants for the cleaning of hard surfaces |
DE3247431A1 (en) * | 1982-12-22 | 1984-06-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR REGENERATION OR FOR RECYCLING AQUEOUS DEGREASING AND CLEANING SOLUTIONS |
EP0249164A1 (en) * | 1986-06-13 | 1987-12-16 | Henkel Kommanditgesellschaft auf Aktien | Cationic surfactants based on quaternary ammonium compounds and their use in detergents |
DE4014859A1 (en) * | 1990-05-09 | 1991-11-14 | Henkel Kgaa | USE OF A COMBINATION OF IONIC AND NON-IONIC SURFACES |
DE19948413A1 (en) * | 1999-10-07 | 2001-04-12 | Unruh Stephan | Cleaning solution of pH 8-12 for degreasing work pieces comprises low concentration of anionic, cationic or nonionic surfactant and water |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1818A (en) * | 1840-10-10 | Machine eoe | ||
DE2556527A1 (en) | 1975-12-16 | 1977-06-30 | Hoechst Ag | Detergent for cleaning metal - contains alkali-stable, low-foam nonionic polyglycol tert.-butyl ether |
DE3315951A1 (en) | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
DE3530623A1 (en) * | 1985-08-28 | 1987-03-12 | Henkel Kgaa | Demulsifying detergent with surface moisturizing effect |
DE3844183A1 (en) * | 1988-12-29 | 1990-07-19 | Metallgesellschaft Ag | AQUEOUS CLEANER FOR METAL SURFACES |
GB8919244D0 (en) * | 1989-08-24 | 1989-10-04 | British Petroleum Co Plc | Method for breaking emulsions |
DE4001595A1 (en) * | 1990-01-20 | 1991-07-25 | Henkel Kgaa | DEMULGATING, POWDERFUL, OR LIQUID CLEANSING AGENTS AND THEIR USE |
DE4107643A1 (en) * | 1991-03-09 | 1992-09-10 | Bayer Ag | METHOD FOR CLEAVING OIL-IN-WATER EMULSIONS |
DK0575355T4 (en) * | 1991-03-12 | 1999-09-27 | Alfred Korcher Gmbh & Co | Demulsifying cleanser |
US5380468A (en) * | 1992-10-20 | 1995-01-10 | Man-Gill Chemical Company | Aqueous alkaline composition for cleaning aluminum and tin surfaces |
US5330656A (en) * | 1993-03-05 | 1994-07-19 | Calgon Corporation | Polysalt compositions and the use thereof for treating an oil and water system |
DE4324396A1 (en) | 1993-07-21 | 1995-01-26 | Henkel Kgaa | Detergents with high wettability |
US5614027A (en) * | 1994-09-23 | 1997-03-25 | Church & Dwight Co., Inc. | Metal cleaner with novel anti-corrosion system |
WO1996009368A1 (en) | 1994-09-23 | 1996-03-28 | Church & Dwight Company, Inc. | Aqueous metal cleaner |
GB9420276D0 (en) * | 1994-10-07 | 1994-11-23 | Burwood Corp The Ltd | Chemically based oil recovery system |
US5712236A (en) | 1995-08-02 | 1998-01-27 | Church & Dwight Co., Inc. | Alkali metal cleaner with zinc phosphate anti-corrosion system |
WO1998024869A1 (en) * | 1996-12-06 | 1998-06-11 | Henkel Corporation | Composition and method for cleaning/degreasing metal surfaces, especially composites of copper and aluminum |
CA2273258A1 (en) | 1996-12-13 | 1998-06-18 | Henkel Corporation | Composition and method for deburring/degreasing/cleaning metal surfaces |
US6124253A (en) | 1997-09-16 | 2000-09-26 | Church & Dwight Co., Inc. | Aqueous composition for low-temperature metal-cleaning and method of use |
USH1818H (en) * | 1997-10-17 | 1999-11-02 | Sasol Technology (Proprietary) Limited | Detergent and cleaning compositions derived from new detergent alcohols |
US5863881A (en) | 1998-02-02 | 1999-01-26 | Citra Science Ltd. | Heavy oil remover |
GB2335661A (en) | 1998-03-26 | 1999-09-29 | Reckitt & Colman Inc | Hard surface cleaners comprising amphoteric surfactant |
US5998352A (en) | 1998-06-23 | 1999-12-07 | Dotolo Research Ltd. | Heavy oil remover |
US6310263B1 (en) | 1999-11-08 | 2001-10-30 | Dotolo Research Ltd. | Heavy oil remover |
US7169192B2 (en) * | 2003-05-02 | 2007-01-30 | Ecolab Inc. | Methods of using heterogeneous cleaning compositions |
CN1283339C (en) * | 2003-09-27 | 2006-11-08 | 中国石油天然气股份有限公司 | Method for preparing multifunctional deemulsifying agent of crude oil and products thereof |
US20050079992A1 (en) | 2003-10-10 | 2005-04-14 | Ecolab Inc. | Cleaning composition and methods |
DE102004057623A1 (en) | 2004-11-29 | 2006-06-01 | Henkel Kgaa | Aqueous cleaning agent concentrate, useful for cleaning oil- and/or fat- polluted metallic surfaces, comprises water, glycol ether and/or non-ionic surfactant, polyethylenimine and cationic surfactant |
DE102006018216B4 (en) | 2006-04-18 | 2008-09-25 | Chemetall Gmbh | Process for the demulsifying cleaning of metallic surfaces |
-
2006
- 2006-04-18 DE DE102006018216A patent/DE102006018216B4/en not_active Revoked
-
2007
- 2007-03-26 ES ES07727340.7T patent/ES2586573T3/en active Active
- 2007-03-26 MX MX2008013310A patent/MX318016B/en active IP Right Grant
- 2007-03-26 WO PCT/EP2007/052867 patent/WO2007122056A1/en active Application Filing
- 2007-03-26 EP EP07727340.7A patent/EP2010696B1/en active Active
- 2007-03-26 ES ES10173888.8T patent/ES2684116T3/en active Active
- 2007-03-26 EP EP10173888.8A patent/EP2253741B1/en active Active
- 2007-03-26 BR BRPI0711624-1A patent/BRPI0711624B1/en active IP Right Grant
- 2007-03-26 US US12/294,111 patent/US20100068392A1/en not_active Abandoned
- 2007-03-26 CN CN201210144323.9A patent/CN102787320B/en active Active
- 2007-03-26 CN CN2007800226913A patent/CN101473068B/en active Active
- 2007-03-26 CA CA2650947A patent/CA2650947C/en active Active
-
2008
- 2008-11-17 ZA ZA2008/09775A patent/ZA200809775B/en unknown
-
2012
- 2012-07-11 US US13/546,317 patent/US8609195B2/en active Active
-
2013
- 2013-10-16 US US14/055,348 patent/US20140041693A1/en not_active Abandoned
-
2014
- 2014-07-02 US US14/322,046 patent/US9731331B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0054895A1 (en) * | 1980-12-23 | 1982-06-30 | Hoechst Aktiengesellschaft | Mixture of surfactants for the cleaning of hard surfaces |
DE3247431A1 (en) * | 1982-12-22 | 1984-06-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR REGENERATION OR FOR RECYCLING AQUEOUS DEGREASING AND CLEANING SOLUTIONS |
EP0249164A1 (en) * | 1986-06-13 | 1987-12-16 | Henkel Kommanditgesellschaft auf Aktien | Cationic surfactants based on quaternary ammonium compounds and their use in detergents |
DE4014859A1 (en) * | 1990-05-09 | 1991-11-14 | Henkel Kgaa | USE OF A COMBINATION OF IONIC AND NON-IONIC SURFACES |
DE19948413A1 (en) * | 1999-10-07 | 2001-04-12 | Unruh Stephan | Cleaning solution of pH 8-12 for degreasing work pieces comprises low concentration of anionic, cationic or nonionic surfactant and water |
Also Published As
Publication number | Publication date |
---|---|
EP2010696B1 (en) | 2016-05-11 |
CN102787320A (en) | 2012-11-21 |
ES2684116T3 (en) | 2018-10-01 |
CA2650947C (en) | 2016-05-24 |
MX318016B (en) | 2014-02-12 |
DE102006018216B4 (en) | 2008-09-25 |
BRPI0711624A2 (en) | 2011-12-06 |
ZA200809775B (en) | 2010-02-24 |
US9731331B2 (en) | 2017-08-15 |
MX2008013310A (en) | 2009-01-09 |
DE102006018216A1 (en) | 2007-10-31 |
US20120273013A1 (en) | 2012-11-01 |
BRPI0711624B1 (en) | 2018-04-03 |
CN101473068B (en) | 2012-07-04 |
EP2010696A1 (en) | 2009-01-07 |
CA2650947A1 (en) | 2007-11-01 |
EP2253741B1 (en) | 2018-05-16 |
WO2007122056A1 (en) | 2007-11-01 |
US20100068392A1 (en) | 2010-03-18 |
EP2253741A2 (en) | 2010-11-24 |
US20140041693A1 (en) | 2014-02-13 |
US20140311533A1 (en) | 2014-10-23 |
CN102787320B (en) | 2014-10-29 |
ES2586573T3 (en) | 2016-10-17 |
CN101473068A (en) | 2009-07-01 |
US8609195B2 (en) | 2013-12-17 |
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