WO2005113691A1 - Entschäumer-zusammensetzungen für wasserverdünnbare lacksysteme - Google Patents
Entschäumer-zusammensetzungen für wasserverdünnbare lacksysteme Download PDFInfo
- Publication number
- WO2005113691A1 WO2005113691A1 PCT/EP2005/005159 EP2005005159W WO2005113691A1 WO 2005113691 A1 WO2005113691 A1 WO 2005113691A1 EP 2005005159 W EP2005005159 W EP 2005005159W WO 2005113691 A1 WO2005113691 A1 WO 2005113691A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- paint systems
- carbon atoms
- glycerides
- diglycerides
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/47—Levelling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
Definitions
- the invention relates to defoamer compositions for water-dilutable paint systems.
- the object of the present invention was to provide defoamer compositions for water-dilutable paint systems.
- defoamers should have the following properties in particular: They should have good defoaming properties, namely
- the defoamers should also solve the task of increasing the stove limit of water-borne stoving lacquers.
- craters small, trough-shaped depressions in lacquer films as craters.
- a special form of craters are the so-called stoves, which are created, for example, in stove enamels in the presence of volatile solvents. When they dry, they evaporate relatively quickly from the upper layers of the paint film, which increases the viscosity on the surface and closes it quickly. The evaporating solvents from the lower layers of paint then form bubbles that burst open and are then already highly viscous paint can no longer be closed. Then pinpricks or craters appear in the dry film. The stove phenomenon also occurs with water-based paint systems.
- the term “stove limit” in the context of the present invention is understood to mean the determined dry layer thickness of the hardened lacquer, up to which no stove bubbles, pinholes or pinholes can be recognized. Only when the critical layer thickness of the hardened lacquer given by the stove boundary is exceeded These undesirable stove phenomena occur.
- the determination of the stove limit is carried out by painting a visible wedge, ie a continuous increase in the layer thickness on a test plate. The increase in the stove limit, i.e.
- the critical dry layer thickness of the lacquer enables the lacquer to be of an appropriate layer thickness can be applied without burn-in of film defects caused by suddenly evaporating water or solvent, which is desirable on the one hand for economic reasons and on the other hand it increases the application safety, because it happens again and again that lacquer manual application is sprayed too thick. Even with automatic application by robots, it can occur due to air swirls, running on vertical surfaces, temperature and viscosity fluctuations as well as in overlapping areas come to higher layer thicknesses. The effect in the finished paint film is then shown in the form of stove bubbles, pinpricks or pinholes.
- a further object was that the defoamers according to the invention should have no negative properties on the paint film (good tolerances), cause no craters, cause no loss of gloss, do not deteriorate the adhesion to the substrate, do not impair the adhesion to the subsequent paint layer, the visual impression ( "Appearance") should not be adversely affected.
- Another object was that the defoamers according to the invention guarantee good flow properties and good substrate wetting of the lacquer treated therewith.
- the present invention therefore relates to defoamer compositions for water-thinnable coating systems comprising a) one or more glycerides, b) one or more ahphatic hydrocarbons and c) one or more addition products of ethylene oxide (EO) and / or propylene oxide (PO) on fatty alcohols with 8 up to 24 carbon atoms, these addition compounds optionally being end group-capped.
- EO ethylene oxide
- PO propylene oxide
- glycerides are understood to mean mono-, di- and tri-esters of glycerol with fatty acids having 8 to 24 carbon atoms.
- monoesters of glycerol with fatty acids as monoglycerides
- diesters of glycerol with fatty acids as diglycerides
- triesters of glycerol with fatty acids are referred to as triglcerides, as is customary in the art.
- the monoesters it does not matter whether the glycerol on which the monoglycerides are based is esterified in the 1- or 2-position.
- diesters it does not matter whether the glycerol on which the diglycerides are based is in the 1- and 2-positions or is esterified in the 1- and 3-position.
- the glycerides can be contained in the compositions according to the invention as such or in the form of technical mixtures. It is characteristic of such technical mixtures that - especially if they are derived from naturally renewable raw materials - they contain fatty acid building blocks of different carbon chain lengths.
- Diglycerides are particularly preferred according to the invention. Such diglycerides of technical quality can also contain mono- and / or triglycerides. It is preferred that the proportion of diglycerides is 20-80% by weight, based on the total amount of mono- / di-, mono- / tri- or mono- / di- / triglycerides. A diglyceride content of 35-70% by weight and in particular 45-60% by weight is preferred.
- the proportion of free glycerol is preferably below 5% by weight, in particular below 3% by weight and very particularly preferably below 1.5% by weight.
- the chain lengths of the fatty acid building blocks in the glycerides are in the range from 8 to 24 carbon atoms. A range of 12 to 18 carbon atoms is preferred.
- the fatty acid building blocks are preferably of natural origin and can be saturated or unsaturated. In one embodiment, those glycerides are used whose fatty acid building blocks are highly unsaturated. Examples of suitable fatty acid building blocks are, for example, fatty acids ex sunflower, rapeseed, soybean, coconut or tall oil. Examples of particularly suitable fatty acid building blocks of the diglycerides are, for example, oleic acid, linoleic acid, linolenic acid and conjugated linoleic acids.
- the aliphatic hydrocarbons (b) can be linear, branched or cyclic. In addition, they can be saturated or mono- or poly-olefinically unsaturated. They may contain a maximum of 18% by weight (based on the total of hydrocarbons) of aromatic hydrocarbons.
- the compounds (b) are preferably low in aromatics and contain less than 1% by weight and in particular less than 0.1% by weight (based on the total of hydrocarbons) of aromatic hydrocarbons.
- the compounds (b) in particular have boiling range limits in the range from 140 to 280 ° C. A range of 170-260 ° C and in particular of 180-240 ° C is preferred.
- End group-locked is to be understood to mean that the free OH group of the adducts of ethylene oxide (EO) and / or propylene oxide (PO) with fatty alcohols with 8 to 24 carbon atoms is present in etherified form, specifically as the radical OR, where R is is an alkyl radical having 1 to 4 carbon atoms or can also be a benzyl radical, R can therefore be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or benzyl, where methyl is and the said butyl radicals are preferred.
- R is is an alkyl radical having 1 to 4 carbon atoms or can also be a benzyl radical
- R can therefore be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or benzyl, where methyl is and the said
- Examples of suitable substances of type c) are, for example, Dehypon LS 24, Dehypon LS 36, Dehypon LS 45, Dehypon LS 54, Dehypon LT 054, Dehypon LS 104 (all commercial products from Cognis GmbH & Co. KG).
- the chain length of the fatty alcohols in the addition products mentioned is preferably 10 to 16 and in particular 12 to 14 C atoms.
- the adducts contain a total of at least 2 mol EO and / or PO per mol fatty alcohol.
- the amount of EO is preferably 0 to 10 and in particular 2 to 5 mol per mol of fatty alcohol.
- the amount of PO is preferably 0 to 10 and in particular 2 to 4 mol per mol of fatty alcohol.
- the adducts preferably contain a total of 2 to 15, in particular 4 to 9, moles of EO and / or PO per mole of fatty alcohol.
- the defoamer compositions for water-dilutable coating systems contain components a), b) and c) described in more detail above. Based on the sum of components a), b) and c) in the defoamer compositions,
- the proportion of component a) preferably 5 to 80% by weight and in particular 20 to 60% by weight,
- the proportion of component c) is preferably 5 to 60% by weight and in particular 10 to 40% by weight.
- the defoamer compositions can also contain additional further components, for example oxo oils, fatty acid esters, silica, waxes, pure and modified silicone oils.
- the defoamer compositions according to the invention are used in water-dilutable paint systems. Investigations by the applicant have surprisingly shown that the stove limit is significantly increased in water-dilutable stoving fillers, namely by more than 20% compared to the corresponding water-thinnable stoving fillers without the addition of the defoamers according to the invention.
- the surface of the paint film has no negative properties (no craters, pinholes, pinholes, no loss of gloss). It is characterized by a good visual appearance ("appearance"). The course of the lacquer is positively improved, which can already be seen visually. Examples
- Hyflo diatomaceous earth flux calcined ("Hyflo Super Cel" from Celite Corporation)
- Fascat tin oxalate ("Fascat 2001" from Atofina)
- Bayhydrol FT 145 water-dilutable fatty acid-modified polyurethane resin (Bayer)
- Maprenal MF 904 hexamethoxymethylmelamine (HMMM) resin (UCB)
- Hydropalat 7003 complex phosphoric acid ester (from Cognis)
- Tronox R-FD-I titanium dioxide rutile (from KerrMcGee)
- the recipes were prepared by first presenting a base lacquer formulation.
- the components of fatty acid diglyceride, aliphatic hydrocarbon and fatty alcohol-EO / PO adduct were added to this basic formulation in the stated amounts by stirring for 15 minutes at 5000 revolutions per minute in a grinding pot with dissolver disc (device: VMA Getzmann) and then for 20 minutes treat in a pearl mill with Teflon grinding disc with glass beads incorporated at 4000 revolutions per minute.
- the specified amounts of the components Bayhydrol D270, distilled water, Marprenal MF 904 and Hydropalat 140 were then added and the mixture was stirred at 1500 revolutions per minute for 10 minutes.
- the pH was finally adjusted in the range from 8.4 to 8.6 with DMEA.
- the viscosity was adjusted using a DIN 4 flow cup to a flow time of 30-32 s with dist. Water set.
- the varnish settings set were painted on a steel plate in a wedge using a gravity cup gun (1.2 mm nozzle, 4 bar atomizing pressure) - the dry layer thickness was in a range from approx. 20 ⁇ m to 60 ⁇ m dry layer thickness. It was then dried under the following drying conditions: n 10 minutes flash off at 20 ° C, 10 minutes at 80 ° C convection oven, 20 minutes at 160 ° C convection oven. After cooling to 20 ° C, the surface was assessed according to the following criteria:
- the cooker limit was visually assessed the limit of the cooker-free layer (ie maximum dry film thickness that is free of craters, pinholes and pinholes) and then the dry film thickness was determined according to DIN EN ISO 2808 using a film thickness measuring device (specified in micrometers).
- Viscosity Determination of the discharge time with discharge cups according to DIN EN ISO 2431 - - - - -
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/569,438 US7893116B2 (en) | 2004-05-21 | 2005-04-12 | Defoaming compositions for water-dilutable paint systems |
JP2007517035A JP2007537849A (ja) | 2004-05-21 | 2005-05-12 | 水溶性塗料系のための消泡剤 |
EP05739706A EP1749069B1 (de) | 2004-05-21 | 2005-05-12 | Entschäumer-zusammensetzungen für wasserverdünnbare lacksysteme |
DE502005007988T DE502005007988D1 (de) | 2004-05-21 | 2005-05-12 | E lacksysteme |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004024947.4 | 2004-05-21 | ||
DE102004024947A DE102004024947B4 (de) | 2004-05-21 | 2004-05-21 | Entschäumer-Zusammensetzungen für wasserverdünnbare Lacksysteme |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005113691A1 true WO2005113691A1 (de) | 2005-12-01 |
Family
ID=34966908
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/005159 WO2005113691A1 (de) | 2004-05-21 | 2005-05-12 | Entschäumer-zusammensetzungen für wasserverdünnbare lacksysteme |
Country Status (6)
Country | Link |
---|---|
US (1) | US7893116B2 (de) |
EP (1) | EP1749069B1 (de) |
JP (1) | JP2007537849A (de) |
DE (2) | DE102004024947B4 (de) |
ES (1) | ES2332658T3 (de) |
WO (1) | WO2005113691A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2186863A1 (de) * | 2008-11-15 | 2010-05-19 | Cognis IP Management GmbH | Verwendung von Anlagerungsprodukten von Ethylen- und/oder Propylenoxid an Fettalkohole als Koaleszenzmittel |
WO2010069568A1 (de) * | 2008-12-20 | 2010-06-24 | Basf Coatings Gmbh | Wässriger beschichtungsstoff, verfahren zu seiner herstellung und seine verwendung |
EP2301645A1 (de) * | 2009-09-28 | 2011-03-30 | Cytec Surface Specialties Austria GmbH | Entschäumer für Airless-Sprüh-Auftrag |
JP2014101428A (ja) * | 2012-11-19 | 2014-06-05 | Kusumoto Kasei Kk | 揮発分のない水性塗料用消泡剤 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6157361B2 (ja) * | 2011-02-09 | 2017-07-05 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングBASF Coatings GmbH | 着色および/または効果付与多層塗装の製造方法 |
JP6584865B2 (ja) * | 2014-08-22 | 2019-10-02 | 花王株式会社 | モノグリセリド含有組成物の製造方法 |
US20240141180A1 (en) * | 2019-10-23 | 2024-05-02 | Basf Coatings Gmbh | Pigmented Aqueous Coating Composition with Improved Stability Towards Pinholes |
KR20220103128A (ko) | 2019-12-03 | 2022-07-21 | 산 노프코 가부시키가이샤 | 소포제 및 수계 코팅 조성물 |
CN114149322A (zh) * | 2021-10-29 | 2022-03-08 | 南京中威生物材料研究院有限公司 | 一种中链脂肪酸单双甘油酯的制备工艺 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19751288A1 (de) * | 1997-11-19 | 1999-05-20 | Henkel Kgaa | Antischaummittel |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2762780A (en) * | 1952-05-07 | 1956-09-11 | Hodag Chemical Corp | Antifoam compositions |
US4880564A (en) * | 1986-09-29 | 1989-11-14 | Ciba-Geigy Corporation | Antifoams for aqueous systems and their use |
DE4135399A1 (de) * | 1991-10-26 | 1993-04-29 | Goldschmidt Ag Th | Copolymerisate auf der basis von vinylethern und propenylpolyethern und deren verwendung als entlueftungsmittel fuer waessrige anstrichsysteme |
DE4211207A1 (de) * | 1992-04-03 | 1993-10-07 | Henkel Kgaa | Verwendung von endgruppenverschlossenen Alkylpolyethylenglykolethern als schauminhibierender Zusatz zu Koagulierungsmitteln |
DE19629038A1 (de) * | 1996-07-19 | 1998-01-22 | Henkel Kgaa | Verwendung von mit alpha-Olefinepoxiden umgesetzten Ethylenoxid/Propylenoxid-Anlagerungsverbindungen des Glycerins oder Polyglycerins als Entschäumer |
JPH1128308A (ja) * | 1997-05-15 | 1999-02-02 | Asahi Denka Kogyo Kk | 消泡剤組成物 |
DE19802733B4 (de) * | 1998-01-26 | 2006-08-24 | Cognis Deutschland Gmbh & Co. Kg | Antischaummittel |
DE19903546A1 (de) * | 1999-01-29 | 2000-08-03 | Basf Ag | Entschäumer und/oder Entlüfter auf der Basis von Öl-in-Wasser-Dispersionen |
DE10233701A1 (de) * | 2002-07-24 | 2004-02-05 | Basf Ag | Entschäumer und/oder Entlüfter für wässrige, zur Schaumbildung neigende Medien |
-
2004
- 2004-05-21 DE DE102004024947A patent/DE102004024947B4/de not_active Expired - Fee Related
-
2005
- 2005-04-12 US US11/569,438 patent/US7893116B2/en active Active
- 2005-05-12 ES ES05739706T patent/ES2332658T3/es active Active
- 2005-05-12 EP EP05739706A patent/EP1749069B1/de active Active
- 2005-05-12 JP JP2007517035A patent/JP2007537849A/ja active Pending
- 2005-05-12 WO PCT/EP2005/005159 patent/WO2005113691A1/de not_active Application Discontinuation
- 2005-05-12 DE DE502005007988T patent/DE502005007988D1/de active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19751288A1 (de) * | 1997-11-19 | 1999-05-20 | Henkel Kgaa | Antischaummittel |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2186863A1 (de) * | 2008-11-15 | 2010-05-19 | Cognis IP Management GmbH | Verwendung von Anlagerungsprodukten von Ethylen- und/oder Propylenoxid an Fettalkohole als Koaleszenzmittel |
WO2010069568A1 (de) * | 2008-12-20 | 2010-06-24 | Basf Coatings Gmbh | Wässriger beschichtungsstoff, verfahren zu seiner herstellung und seine verwendung |
US20110256319A1 (en) * | 2008-12-20 | 2011-10-20 | Basf Coatings Gmbh | Aqueous coating substance, method for the production thereof, and use thereof |
EP2301645A1 (de) * | 2009-09-28 | 2011-03-30 | Cytec Surface Specialties Austria GmbH | Entschäumer für Airless-Sprüh-Auftrag |
WO2011036039A1 (en) * | 2009-09-28 | 2011-03-31 | Cytec Austria Gmbh | Defoamers for airless paint spray application |
US9017471B2 (en) | 2009-09-28 | 2015-04-28 | Allnex Austria Gmbh | Defoamers for airless paint spray application |
JP2014101428A (ja) * | 2012-11-19 | 2014-06-05 | Kusumoto Kasei Kk | 揮発分のない水性塗料用消泡剤 |
Also Published As
Publication number | Publication date |
---|---|
US20080021117A1 (en) | 2008-01-24 |
US7893116B2 (en) | 2011-02-22 |
EP1749069A1 (de) | 2007-02-07 |
JP2007537849A (ja) | 2007-12-27 |
DE102004024947A1 (de) | 2005-12-15 |
EP1749069B1 (de) | 2009-08-26 |
DE502005007988D1 (de) | 2009-10-08 |
DE102004024947B4 (de) | 2006-12-07 |
ES2332658T3 (es) | 2010-02-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1749069B1 (de) | Entschäumer-zusammensetzungen für wasserverdünnbare lacksysteme | |
DE2806497C2 (de) | Mehrschichtlackierung mit einem Klarlacküberzug als Schlußschicht | |
EP2421924B1 (de) | Wasserfreie high-solid-basislacke, ihre herstellung und ihre verwendung zur herstellung von mehrschichtlackierungen, sowie mehrschichtlackierungen enthaltend eine basislackierung aus einem wasserfreien high-solid-basislack | |
EP0578645B1 (de) | Verfahren zur herstellung von autoreparaturlacken | |
EP2167595B1 (de) | Verfahren zum aufbringen von korrosionsschutzschichten auf metallische oberflächen | |
EP2142606B1 (de) | Verwendung von estern als koaleszenzmittel | |
EP3402852A1 (de) | Carboxyfunktionelle polyether-basierte reaktionsprodukte und wässrige basislacke enthaltend die reaktionsprodukte | |
EP0069936A2 (de) | Verfahren zur Herstellung von stabilen wässrigen Dispersionen und deren Verwendung als Bindemittel zur Herstellung von Lacken, insbesondere Zweischicht-Metalleffekt-Lacksystemen | |
WO2008141768A1 (de) | Wässrige, pigmentierte beschichtungsmittel, verfahren zu deren herstellung und deren verwendung zur herstellung von mehrschichtlackierungen | |
DE3238864C2 (de) | Wäßrige Harzmasse | |
DE102008064254A1 (de) | Wässriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung | |
DE3223411C2 (de) | Zinkreicher Lack unter Verwendung von Mangan(II,III)-Oxid als Pigment | |
EP2208544A1 (de) | Kombinationsbeschichtung für Holz | |
DE3223410C2 (de) | Lösungsmittelhaltiger Lack mit Farbpigment | |
DE3918980C2 (de) | ||
DE102005021599A1 (de) | Verfahren zur Erzeugung mehrschichtiger Beschichtungen, und die so erhaltenen mehrschichtigen Beschichtungen | |
DE1669137C3 (de) | Anstrichmittel mit thixotropen Eigenschaften | |
CH635611A5 (de) | Verfahren zur herstellung von waessrigen harzdispersionen. | |
EP0553663B1 (de) | Verfahren zur Herstellung von thixotropen Lackbindemitteln auf Alkydharzbasis | |
EP1389627A1 (de) | Polyurethan-Mikrogel | |
DE2621531A1 (de) | Oberflaechenbeschichtung und verfahren zum aufbringen derselben | |
DE3922702A1 (de) | Lufttrocknende alkydharze sowie ihre verwendung in beschichtungsmitteln, insbesondere fuer die beschichtung von holz | |
DE102007038487A1 (de) | Wässriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung | |
DE3323845C2 (de) | ||
EP0560783B1 (de) | Beschichtungsmittel mit hohem feststoffgehalt, verfahren zur herstellung davon und verwendung der beschichtungsmittel zur decklackierung und als grundierung im industriebereich |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005739706 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11569438 Country of ref document: US Ref document number: 2007517035 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWP | Wipo information: published in national office |
Ref document number: 2005739706 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11569438 Country of ref document: US |