WO1992014763A1 - Verfahren zur herstellung eines wässrigen, autoxidativ trocknenden emulsionspolymerisates vorzugsweise als bindemittel für lacke - Google Patents

Verfahren zur herstellung eines wässrigen, autoxidativ trocknenden emulsionspolymerisates vorzugsweise als bindemittel für lacke Download PDF

Info

Publication number
WO1992014763A1
WO1992014763A1 PCT/DE1992/000107 DE9200107W WO9214763A1 WO 1992014763 A1 WO1992014763 A1 WO 1992014763A1 DE 9200107 W DE9200107 W DE 9200107W WO 9214763 A1 WO9214763 A1 WO 9214763A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
polymer
solution polymer
solution
mass
Prior art date
Application number
PCT/DE1992/000107
Other languages
German (de)
English (en)
French (fr)
Inventor
Karl-Heinz Weinert
Siegfried Müller
Hans-Joachim Lorkowski
Doris Zekai
Klaus Tauer
Original Assignee
Lankwitzer Lackfabrik Gmbh. & Co. Kg
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lankwitzer Lackfabrik Gmbh. & Co. Kg filed Critical Lankwitzer Lackfabrik Gmbh. & Co. Kg
Publication of WO1992014763A1 publication Critical patent/WO1992014763A1/de

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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of acids or salts

Definitions

  • the invention relates to a process for producing an aqueous, autoxidatively drying emulsion polymer, preferably as a binder for lacquers, in which "a solution polymer containing carboxyl groups is first prepared by polymerizing an addition product from unsaturated fatty acids and unsaturated monomers, and then an emulsion polymerization of unsaturated monomers is carried out together with this solution polymer.
  • binder dispersions disclosed in US Pat. No. 4,122,052 show poor results in terms of gloss and toughness. Furthermore, these polymers contain too much organic solvents. as well as ammonia or amine, so that when used as a coating material they still represent strong environmental hazards.
  • the emulsifier is a maleic acid adduct of an alkyd resin. Disadvantages of such systems are the deepening of the color of the products caused by the formation of maleic acid adduct and the inadequate compatibility between the emulsifier and the polymer formed with the vinyl monomers.
  • the object of the invention is to carry out the process mentioned at the outset in such a way that better products are obtained in comparison with the known solutions.
  • This object is achieved by a process for producing an aqueous, autoxidatively drying emulsion polymer
  • an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid and maleic anhydride, alone or in combination, where
  • the solution polymer has an acid number between 20 and 160 and a number average molecular weight M ,, of 1,500 to 80,000 and the unsaturated fatty acid (s) form 15-60% by mass of the solution polymer,
  • the solution polymer fulfills two functions:
  • the two functions of the solution polymer are influenced by the degree of neutralization of the carboxyl groups:
  • the solubility of the solution polymer is reduced, so that it can only act insufficiently as a dispersion stabilizer. If the degree of neutralization is too high, the solubility increases such that not only is the dynamic equilibrium of the distribution of the solution polymer between the interior of the solution and the phase boundary regions monomer / water or polymer / water shifted in favor of the interior of the solution, but also at the same time due to the increased degree of dissociation of the carboxyl group, the polymer molecules expand. The latter behavior can even increase the viscosity to such an extent that conventional emulsion polymerization is prevented or unsuitable cream-like products are formed.
  • the dispersed polymer particles surprisingly have a core-shell morphology, the unsaturated fatty acids introduced via the solution polymer being enriched in the shell region.
  • the polymer particles penetrate and bond mainly with their shell areas. These determine the properties of the overall film.
  • This morphology requires a degree of neutralization that is neither 0 nor 1. With one between these Accordingly, the two degrees of neutralization have particularly good properties.
  • the lacquers which are produced according to the teaching according to the invention are more weather-resistant, storage-stable, light-resistant, shear-stable, glossy and harder than the lacquers which are produced by the known processes.
  • the binders according to the invention contain less amines or ammonia.
  • the binders according to the invention are notable for high water, in particular salt water and solvent resistance.
  • the conversion to the addition product from unsaturated fatty acids and unsaturated monomers, preferably glycidyl methacrylate, is usually carried out at a temperature of 120 to 190 ° C., preferably at a temperature of 150 ° C., and with the catalyst tetraethylammonium bromide in a time of 1 to 6 hours, preferably 2 hours.
  • the acid number of the mixture drops below 3% of the initial value after the reaction.
  • the solution polymer is preferably synthesized by free-radical polymerization of the addition product with unsaturated carboxylic acids, preferably with methacrylic acid in cyclohexanone or butoxyethanol at 90 ° to 150 ° C., preferably at 120 ° C. in butoxyethanol, with the aid of azo initiators.
  • the content of carboxylic acid must not be too high, but also not too low. A minimum value must be reached in order for the solution polymer to be sufficiently water-soluble, and a maximum value must not be exceeded so that the finished coating remains sufficiently hydrophobic.
  • the proportion of methacrylic acid in the solution polymer is preferably 20% by mass.
  • the emulsion polymerization is carried out at temperatures from 60 ° to 80 ° C., preferably 70 ° C.
  • the monomers are reacted under nitrogen without first removing any inhibitor that may be present.
  • Ammonium peroxodisulfate is preferably used as the water-soluble radical initiator.
  • the use of an external emulsifier can be dispensed with, since its function is essentially carried out by the solution polymer.
  • the anionic emulsifier sodium alkyl sulfate is preferably used.
  • external emulsifiers are those which are incorporated in the course of the emulsion polymerization.
  • Monosodium sulfopropyl monododecyl maleate is preferably used.
  • tetraethylammonium bromide 0.25 g are dissolved in 131.5 g of glycidyl methacrylate (GMA), which contains 0.005% by mass of hydroquinone monoethyl ether, and then mixed with 250 g of soybean oil fatty acid. The mixture is melted under nitrogen in an ampoule and heated in an oil bath at 155 ° C. for 90 minutes. The conversion of the carboxyl groups is checked by gas chromatography by determining the acid number or that of the GMA. The monomer (1.1) obtained has an acid number below 3% of the initial value.
  • GMA glycidyl methacrylate
  • the product (1.3) is mixed with 4.4 g of sodium dodecyl sulfate, 68 g of methyl methacrylate and 250 g of n-butyl methacrylate, and an emulsion is prepared under vigorous stirring under nitrogen. After heating to 70 ° C., 0.86 g of ammonium peroxodisulfate, dissolved in 20 ml of water, are added to the emulsion and the reaction is ended after 7 hours.
  • the polymer particles have an average size of 220 nm.
  • Example 2 The polymer dispersions are prepared analogously to that of Example 1, except that instead of the 52.2 g of methacrylic acid in stage 1.2, 80.7 g of methacrylic acid and Example 3 67.5 g of acrylic acid are used in Example 2. Because of the increase in the acid content, the proportion of ammonia solution is increased from 9.3 to 13.4 ml in the neutralization stage.
  • the particle sizes reach an average value of 70 nm, in example 3 this is 280 nm.
  • the polymer dispersion is prepared analogously to that of Example 2, only 68 g of styrene are used instead of 68 g of methyl methacrylate in stage 1.4.
  • the particle sizes have an average value of 230 nm.
  • the polymer dispersion is prepared analogously to that of Example 4, except that 67.5 g of acrylic acid are used instead of methacrylic acid in stage 1.2 and 13.4 ml of ammonia solution in stage 1.3.
  • the particle sizes have an average value of 310 nm.
  • the polymer dispersion is prepared analogously to that of Example 2, except that the emulsifier instead of the 4.4 g Na dodecyl sulfate used the same amount of monosodium sulfopropyl monododecyl maleate.
  • the particle sizes have an average value of 85 nm.
  • emulsion polymers according to the invention can also be used in other cases and not only for lacquers, for example for floor care products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/DE1992/000107 1991-02-15 1992-02-13 Verfahren zur herstellung eines wässrigen, autoxidativ trocknenden emulsionspolymerisates vorzugsweise als bindemittel für lacke WO1992014763A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914105134 DE4105134C1 (enrdf_load_stackoverflow) 1991-02-15 1991-02-15
DEP4105134.3 1991-02-15

Publications (1)

Publication Number Publication Date
WO1992014763A1 true WO1992014763A1 (de) 1992-09-03

Family

ID=6425391

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1992/000107 WO1992014763A1 (de) 1991-02-15 1992-02-13 Verfahren zur herstellung eines wässrigen, autoxidativ trocknenden emulsionspolymerisates vorzugsweise als bindemittel für lacke

Country Status (2)

Country Link
DE (1) DE4105134C1 (enrdf_load_stackoverflow)
WO (1) WO1992014763A1 (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643080A3 (de) * 1993-09-10 1995-06-28 Hoechst Ag Polymermischungen mit Wasser.
WO1997031044A1 (en) * 1996-02-22 1997-08-28 The Dexter Corporation Water-dispersible polymer and coating composition containing the same
WO2012028627A1 (de) * 2010-09-01 2012-03-08 Basf Se Wässrige emulsionspolymerisate, deren herstellung und verwendung
US8722756B2 (en) 2010-09-01 2014-05-13 Basf Se Aqueous emulsion polymers, their preparation and use
EP3088432A1 (en) 2015-04-27 2016-11-02 ALLNEX AUSTRIA GmbH Aqueous dispersions
WO2023057249A1 (en) 2021-10-04 2023-04-13 Basf Se Use of aqueous polymer compositions as stains for porous materials

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1009254C2 (nl) * 1998-05-25 1999-11-26 Univ Eindhoven Tech Poederverf.
DE10015913A1 (de) * 1999-04-16 2000-10-19 Henkel Kgaa Fettchemische Addukte als Tackifier und Bindemittel
US7235603B2 (en) * 2003-04-07 2007-06-26 Rohm And Haas Company Ambient curable polymer
DE102007048192A1 (de) 2007-10-08 2009-04-09 Evonik Röhm Gmbh Emulsionspolymere, wässrige Dispersionen und Verfahren zu deren Herstellung
DE102007048189A1 (de) 2007-10-08 2009-04-09 Evonik Röhm Gmbh Wässrige Dispersionen aufweisend mindestens ein Alkyd-Harz und mindestens ein Polymerisat mit mindestens einem (Meth)acrylat-Segment
DE102008002254A1 (de) 2008-06-06 2010-01-21 Evonik Röhm Gmbh Monomermischungen, Polymere sowie Beschichtungszusammensetzungen
DE102009001217A1 (de) 2009-02-27 2010-09-02 Evonik Röhm Gmbh Monomermischungen, Polymere sowie Beschichtungszusammensetzungen
DE102008002257A1 (de) 2008-06-06 2010-01-28 Evonik Röhm Gmbh Wässrige Dispersionen aufweisend mindestens ein Alkyd-Harz
DE102008046075A1 (de) 2008-09-08 2010-03-11 Evonik Röhm Gmbh (Meth)acrylatmonomer, Polymer sowie Beschichtungsmittel
DE102009001966A1 (de) 2009-03-30 2010-10-07 Evonik Röhm Gmbh Beschichtungszusammensetzung,(Meth)acryl-Polymer und Monomermischung zur Herstellung des(Meth)acryl-Polymers
DE102009001965A1 (de) 2009-03-30 2010-10-07 Evonik Röhm Gmbh Beschichtungsmittel, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand
DE102009001964A1 (de) 2009-03-30 2010-10-07 Evonik Röhm Gmbh Multifunktionales(Meth)acryl-Polymer, Beschichtungszusammensetzung, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand
DE102009001970A1 (de) 2009-03-30 2010-10-14 Evonik Röhm Gmbh (Meth)acrylat-Polymer, Beschichtungsmittel, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand
DE102009002888A1 (de) 2009-05-07 2010-11-11 Evonik Röhm Gmbh Beschichtungsmittel, Verfahren zur Herstellung einer Beschichtung und beschichteter Gegenstand
DE102010029930A1 (de) 2010-06-10 2011-12-15 Evonik Röhm Gmbh Verfahren zur Herstellung von Acetoacetoxyalkyl(meth)acrylat
DE102010030970A1 (de) 2010-07-06 2012-01-12 Evonik Röhm Gmbh Zusammensetzung zur Herstellung von Polymeren, (Meth)acryl-Polymer, Beschichtungsmittel und Beschichtung
DE102010041272A1 (de) 2010-09-23 2012-03-29 Evonik Röhm Gmbh Beschichtungsmittel mit (Meth)acryl-Polymeren und Koaleszenzhilfsmitteln
DE102011088149A1 (de) 2011-12-09 2013-06-13 Evonik Industries Ag Beschichteter Verbundkörper, umfassend ein Verbundmaterial
DE102013223876A1 (de) 2013-11-22 2015-05-28 Evonik Industries Ag Emulsionspolymere, wässrige Dispersionen und Verfahren zu deren Herstellung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2265833A1 (enrdf_load_stackoverflow) * 1974-03-28 1975-10-24 Kansai Paint Co Ltd
JPS52102390A (en) * 1976-02-25 1977-08-27 Kansai Paint Co Ltd Preparation of colloidal emulsions
US4122052A (en) * 1976-03-09 1978-10-24 Kansai Paint Company, Limited Emulsion composition
EP0305795A2 (de) * 1987-09-03 1989-03-08 Vianova Kunstharz Aktiengesellschaft Verfahren zur Herstellung von wässrigen Pfropfcopolymerisat- emulsionen und Verwendung der Emulsionen als Bindemittel für lufttrocknende wasserverdünnbare Anstrichmittel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2265833A1 (enrdf_load_stackoverflow) * 1974-03-28 1975-10-24 Kansai Paint Co Ltd
JPS52102390A (en) * 1976-02-25 1977-08-27 Kansai Paint Co Ltd Preparation of colloidal emulsions
US4122052A (en) * 1976-03-09 1978-10-24 Kansai Paint Company, Limited Emulsion composition
EP0305795A2 (de) * 1987-09-03 1989-03-08 Vianova Kunstharz Aktiengesellschaft Verfahren zur Herstellung von wässrigen Pfropfcopolymerisat- emulsionen und Verwendung der Emulsionen als Bindemittel für lufttrocknende wasserverdünnbare Anstrichmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX LATEST, Woche 7740, Derwent Publications Ltd. , Londen, GB; AN-77-71802Y, & JP, A, 52102390 (KANSAI PAINT K.K.) 27. August 1977, siehe Zusammenfassung (in der Anmeldung erwähnt) *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643080A3 (de) * 1993-09-10 1995-06-28 Hoechst Ag Polymermischungen mit Wasser.
US5521267A (en) * 1993-09-10 1996-05-28 Hoechst Aktiengesellschaft Mixtures of polymers with water
WO1997031044A1 (en) * 1996-02-22 1997-08-28 The Dexter Corporation Water-dispersible polymer and coating composition containing the same
US5830952A (en) * 1996-02-22 1998-11-03 The Dexter Corporation Water-dispersible polymer and coating composition containing the same
US5869552A (en) * 1996-02-22 1999-02-09 The Dexter Corporation Water-dispersible polymer and coating composition containing the same
US5922817A (en) * 1996-02-22 1999-07-13 The Dexter Corporation Water-dispersible polymer and coating composition containing the same
AU715870B2 (en) * 1996-02-22 2000-02-10 Dexter Corporation, The Water-dispersible polymer and coating composition containing the same
WO2012028627A1 (de) * 2010-09-01 2012-03-08 Basf Se Wässrige emulsionspolymerisate, deren herstellung und verwendung
US8722756B2 (en) 2010-09-01 2014-05-13 Basf Se Aqueous emulsion polymers, their preparation and use
US9150732B2 (en) 2010-09-01 2015-10-06 Basf Se Aqueous emulsion polymers, their preparation and use
EP3088432A1 (en) 2015-04-27 2016-11-02 ALLNEX AUSTRIA GmbH Aqueous dispersions
WO2016173821A1 (en) 2015-04-27 2016-11-03 Allnex Austria Gmbh Aqueous dispersions
CN107428889A (zh) * 2015-04-27 2017-12-01 湛新奥地利有限公司 含水分散体
KR20170141201A (ko) * 2015-04-27 2017-12-22 알넥스 오스트리아 게엠베하 수성 분산물
US20180086936A1 (en) * 2015-04-27 2018-03-29 Allnex Austria Gmbh Aqueous dispersions
US10494541B2 (en) 2015-04-27 2019-12-03 Allnex Austria Gmbh Aqueous dispersions
AU2016254105B2 (en) * 2015-04-27 2020-01-23 Allnex Austria Gmbh Aqueous dispersions
TWI685551B (zh) * 2015-04-27 2020-02-21 奧地利商湛新奧地利有限公司 水性分散液、其製備方法、摻合物及製備塗布的基材或物件之方法
KR102382413B1 (ko) 2015-04-27 2022-04-01 알넥스 오스트리아 게엠베하 수성 분산물
WO2023057249A1 (en) 2021-10-04 2023-04-13 Basf Se Use of aqueous polymer compositions as stains for porous materials

Also Published As

Publication number Publication date
DE4105134C1 (enrdf_load_stackoverflow) 1992-10-08

Similar Documents

Publication Publication Date Title
WO1992014763A1 (de) Verfahren zur herstellung eines wässrigen, autoxidativ trocknenden emulsionspolymerisates vorzugsweise als bindemittel für lacke
DE69504650T2 (de) Verfahren zur herstellung von wässrigen polymer-zusammensetzungen
DE69406294T2 (de) Herstellung von polymeremulsionen
DE68927530T2 (de) Stabile Emulsionspolymere und Verfahren zu deren Herstellung
DE69501953T2 (de) Herstellung von wässrigen polymerzusammensetzungen
DE69508038T2 (de) Hydroxyfunctionelle Acrylatharze, Verfahren zu deren Herstellung und deren Reaktionsprodukte
EP0072979B1 (de) Wasserverdünnbare Harzzubereitungen auf Basis von Alkydharzen und Polyacrylatharzen sowie deren Verwendung als Lackbindemittel
DE69917280T2 (de) Verfahren zur herstellung von polymeren durch ein freies radikal verfahren, polymerisations- und condensationsreaktion und apparat dafür sowie hergestellte produkte
EP0568834B1 (de) Wässrige Polymerisatdispersion
DE2921811C2 (enrdf_load_stackoverflow)
DE4213965A1 (de) Waessrige polymerisatdispersion
DE1595481A1 (de) Verfahren zur Herstellung polymerer Latices
DE19609509A1 (de) Wäßrige Polymerdispersion als Bindemittel für elastische block- und kratzfeste Beschichtungen
DE3147008A1 (de) Verfahren zur herstellung von waessrigen, hochkonzentrierten bimodalen kunststoffdispersionen
DE2758626A1 (de) Verfahren zum dispergieren eines festen pigments in einem waessrigen medium
DE3789329T2 (de) Verbundstoff-Teilchen aus Akrylharz.
DE19505039A1 (de) Verfahren zur Herstellung von emulgatorfreien wäßrigen Polymerdispersionen
EP0808333A1 (de) Mikrogel
DE68928225T2 (de) Wässrige Anstrichzusammensetzung
DE2422043B2 (de) Verfahren zur Herstellung von Copolymerisaten
EP0121759B1 (de) Verfahren zur Herstellung lagerstabiler Plastisole und Organosole
DE3780351T2 (de) Teilchen aus verbundstoff und ihre herstellung.
DE3888774T2 (de) Nichtwässrige Dispersion, Verfahren zu deren Herstellung und Anwendung.
WO2006000342A1 (de) Plastisole auf basis eines methylmethacrylat-mischpolymerisats
DE69509656T2 (de) Katalytische zusammensetzungen und daraus hergestellte beschichtungen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
EX32 Extension under rule 32 effected after completion of technical preparation for international publication

Ref country code: UA

LE32 Later election for international application filed prior to expiration of 19th month from priority date or according to rule 32.2 (b)

Ref country code: UA

LE32 Later election for international application filed prior to expiration of 19th month from priority date or according to rule 32.2 (b)

Ref country code: UA

122 Ep: pct application non-entry in european phase