EP2164821A1 - Melange de materiaux et procede de conservation de materiaux poreux - Google Patents
Melange de materiaux et procede de conservation de materiaux poreuxInfo
- Publication number
- EP2164821A1 EP2164821A1 EP08759298A EP08759298A EP2164821A1 EP 2164821 A1 EP2164821 A1 EP 2164821A1 EP 08759298 A EP08759298 A EP 08759298A EP 08759298 A EP08759298 A EP 08759298A EP 2164821 A1 EP2164821 A1 EP 2164821A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixture
- ormosil
- composition according
- substance
- added
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 239000011148 porous material Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000004575 stone Substances 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 150000004756 silanes Chemical class 0.000 claims abstract description 5
- 239000002023 wood Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- 150000002118 epoxides Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- GUUFUSNFDFBVIQ-UHFFFAOYSA-N CCC[Si](OC)(OC)OCCC1CO1 Chemical compound CCC[Si](OC)(OC)OCCC1CO1 GUUFUSNFDFBVIQ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 silica ester Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
Definitions
- the invention relates to a methylmethacrylate-free mixture for preserving porous substances, in particular objects made of stone or wood. Furthermore, the invention relates to a method for preserving porous substances.
- TEOS tetraethoxysilane
- KSE silica ester
- the object of the invention is to produce a resistant protective layer in the pore system against the attack of water and pollutants in porous materials, in particular bodies and at the same time build up missing binder in the pore system.
- the mixture contains at least two substances from the group of organically modified silicas, in particular organo (alkoxy) silanes (Ormosile).
- the substance mixtures have a very good penetration behavior due to their molecular size and are able to achieve even very small pores.
- these mixtures harden by hydrolysis and polycondensation, so that a solids content between 4% up to 69%, in particular between 8% to 30% remains as a film lining the pore walls in the pore space.
- the curing which takes place by means of hydrolysis and polycondensation is surprisingly easy to control, in particular in the case of large-volume objects, by means of a program-controlled temperature and moisture control.
- the resulting silica in the pore space verifiably covers the pore walls as a crack-free, transparent, water-insoluble film with good adhesion, so that the hoped-for lining effect of the pore occurs.
- the required water can be added just before the impregnation, without affecting the penetration in the required penetration more negative.
- a coupling agent in particular an organosilane. It is also important that a liquid acrylate-free mixture is achieved.
- the liquid composition according to the invention is used for the preservative impregnation of porous substances, in particular of objects made of wood or stone.
- the two components of the active ingredient system consisting of glycidyl-propyltrimethoxysilane (GLYMO) and aminopropyltriethoxysilane (APTS) in alcoholic solution are combined in stoichiometric amounts before injection into the pore system of the substance to be preserved and react with elimination of water to form an intermediate with six alkoxigram groups.
- Partial hydrolysis activates the active substance system and condenses, with elimination of water and alcohol, to form a silica gel, in whose structure the organic component is bound between Si atoms, and acts as a spacer to build up a low-stress gel structure (Figure).
- the preserving liquid may be composed differently, wherein the mixture contains at least one substance from the group of organo (alkosy) silanes (Ormosile).
- the following mixtures are particularly advantageous:
- a substance of the mixture is an Ormosil containing at least one epoxide unit.
- One substance of the mixture is a 3-glycidyloxypropyltrimethoxysilane (GLYMO).
- GLYMO 3-glycidyloxypropyltrimethoxysilane
- a substance of the mixture is an Ormosil containing at least one amine function.
- One substance of this mixture is a gammaaminopropyltriethoxysilane (APTS).
- APTS gammaaminopropyltriethoxysilane
- alcohol having one to six carbon atoms especially ethanol or methanol, is added.
- the mass ratio of the Ormosil containing at least one epoxide moiety to the Ormosil containing at least one amine function is 1: 0.2 to 1:10, preferably 1: 0.7 to 1: 1, 7, and more preferably a mass ratio of 1 : 1, 07 on.
- the porous substance in the form of an object eg. As a stone or a piece of wood, is first dried and then immersed in a liquid which consists of at least two Ormosilen plus a solvent liquid preferably ethanol.
- a liquid which consists of at least two Ormosilen plus a solvent liquid preferably ethanol.
- the mass ratio of the Ormosil, which contains at least one epoxide unit to the Ormosil, which contains at least one amine function 1: 1, 07th
- An advantageous mixture consists of 2.4 g Ormosil 1, 2.3 g Ormosil 2 and 28 g ethanol. In the case of 28 g of ethanol, a solids separation of approx. 9.5 - approx. 10% is achieved in the object.
- the proportion of ethanol can be chosen here between 0 - 5O g.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Forests & Forestry (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Polymers (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007030672.7A DE102007030672B4 (de) | 2007-07-02 | 2007-07-02 | Verfahren zum Konservieren poröser Stoffe |
PCT/EP2008/004968 WO2009003594A1 (fr) | 2007-07-02 | 2008-06-20 | Mélange de matériaux et procédé de conservation de matériaux poreux |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2164821A1 true EP2164821A1 (fr) | 2010-03-24 |
Family
ID=39768858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08759298A Withdrawn EP2164821A1 (fr) | 2007-07-02 | 2008-06-20 | Melange de materiaux et procede de conservation de materiaux poreux |
Country Status (9)
Country | Link |
---|---|
US (1) | US20100139522A1 (fr) |
EP (1) | EP2164821A1 (fr) |
JP (1) | JP2010531902A (fr) |
KR (1) | KR20100032869A (fr) |
CN (1) | CN101801889A (fr) |
CA (1) | CA2691909C (fr) |
DE (1) | DE102007030672B4 (fr) |
RU (1) | RU2010103205A (fr) |
WO (1) | WO2009003594A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007041487A1 (de) * | 2007-08-31 | 2009-03-05 | Ibach Steinkonservierung Gmbh & Co. Kg | Stoffmischung als Bindemittel zur Herstellung eines Mörtels |
KR101557497B1 (ko) * | 2008-07-23 | 2015-10-06 | 삼성전자주식회사 | 물질 조성의 구배를 갖는 박막 및 그의 제조방법 |
CN101831076B (zh) * | 2010-04-23 | 2012-07-04 | 华东理工大学 | 硅胶颗粒表面青蒿素分子印迹聚合物及其制备和应用方法 |
EP2971242B1 (fr) * | 2013-03-14 | 2020-05-13 | United Technologies Corporation | Matière de protection contre la corrosion et procédé de protection de revêtements d'aluminium |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385108A2 (fr) * | 1989-02-25 | 1990-09-05 | Degussa Ag | Mélanges contenant des composés organosilicium et leur utilisation pour des imprégnations hydrophobes et antimicrobiennes |
EP0683022A2 (fr) * | 1994-05-16 | 1995-11-22 | Dow Corning Corporation | Compositions hydrofuges |
DE102005010157A1 (de) * | 2005-03-02 | 2006-09-07 | Degussa Ag | Gesteine mit erhöhter Lichttransmission, Verfahren zu ihrer Herstellung und ihre Verwendung |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US254178A (en) * | 1882-02-28 | perk van lith | ||
DE2258901B2 (de) * | 1972-12-01 | 1980-11-06 | Dynamit Nobel Ag, 5210 Troisdorf | Imprägnieren von Mauerwerk mit neutral oder sauer reagierenden Oberflächen |
US5051129A (en) * | 1990-06-25 | 1991-09-24 | Dow Corning Corporation | Masonry water repellent composition |
DE4033155A1 (de) * | 1990-10-12 | 1992-04-16 | Nuenchritz Chemie Gmbh | Hydrophobier- bzw. isoliermittel auf siliconbasis |
DE19816973A1 (de) * | 1998-04-17 | 1999-11-25 | Degussa | Verfahren zur Imprägnierung von mineralischen Baustoffen und dafür geeignete Organosiliciumverbindungen |
DE19904133B4 (de) * | 1999-02-03 | 2007-02-08 | Degussa Ag | Oberflächenmodifizierter Isolator und Verfahren zur Modifizierung der Oberfläche eines Isolators |
DE10044216A1 (de) * | 2000-09-07 | 2002-05-02 | Fraunhofer Ges Forschung | Beschichtungsmaterial für multifunktionelle, superphobe Schichten |
DE10122627A1 (de) * | 2001-05-10 | 2002-11-21 | Wacker Chemie Gmbh | Verfahren zur hydrophobierenden Holzbehandlung |
DE10122626A1 (de) * | 2001-05-10 | 2002-06-06 | Wacker Chemie Gmbh | Verfahren zur hydrophobierenden Holzbehandlung |
DE10130091B4 (de) * | 2001-06-21 | 2007-10-11 | Remmers Baustofftechnik Gmbh | Verfahren zur Herstellung einer gebrauchsfertigen Injektionscreme zur Hydrophobierung von Mauerwerk und deren Verwendung |
DE102004036073A1 (de) * | 2004-07-24 | 2006-02-16 | Degussa Ag | Verfahren zur Versiegelung von Natursteinen |
US20060181774A1 (en) * | 2005-02-16 | 2006-08-17 | Konica Minolta Opto, Inc. | Antireflection film, production method of the same, polarizing plate and display |
-
2007
- 2007-07-02 DE DE102007030672.7A patent/DE102007030672B4/de not_active Expired - Fee Related
-
2008
- 2008-06-20 EP EP08759298A patent/EP2164821A1/fr not_active Withdrawn
- 2008-06-20 CN CN200880021745A patent/CN101801889A/zh active Pending
- 2008-06-20 CA CA2691909A patent/CA2691909C/fr not_active Expired - Fee Related
- 2008-06-20 KR KR1020097027675A patent/KR20100032869A/ko not_active Application Discontinuation
- 2008-06-20 WO PCT/EP2008/004968 patent/WO2009003594A1/fr active Application Filing
- 2008-06-20 JP JP2010513728A patent/JP2010531902A/ja not_active Withdrawn
- 2008-06-20 RU RU2010103205/03A patent/RU2010103205A/ru not_active Application Discontinuation
- 2008-06-20 US US12/665,976 patent/US20100139522A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0385108A2 (fr) * | 1989-02-25 | 1990-09-05 | Degussa Ag | Mélanges contenant des composés organosilicium et leur utilisation pour des imprégnations hydrophobes et antimicrobiennes |
EP0683022A2 (fr) * | 1994-05-16 | 1995-11-22 | Dow Corning Corporation | Compositions hydrofuges |
DE102005010157A1 (de) * | 2005-03-02 | 2006-09-07 | Degussa Ag | Gesteine mit erhöhter Lichttransmission, Verfahren zu ihrer Herstellung und ihre Verwendung |
Non-Patent Citations (1)
Title |
---|
See also references of WO2009003594A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20100139522A1 (en) | 2010-06-10 |
RU2010103205A (ru) | 2011-08-10 |
JP2010531902A (ja) | 2010-09-30 |
DE102007030672A1 (de) | 2009-01-08 |
KR20100032869A (ko) | 2010-03-26 |
CA2691909A1 (fr) | 2009-01-08 |
CN101801889A (zh) | 2010-08-11 |
DE102007030672B4 (de) | 2017-05-24 |
WO2009003594A1 (fr) | 2009-01-08 |
CA2691909C (fr) | 2013-06-18 |
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